Alumina-zirconia, and methods of making and using the same

ABSTRACT

Alumina-zirconia materials and methods of making the same. Embodiments of the invention include abrasive particles. The abrasive particles can be incorporated into a variety of abrasive articles, including bonded abrasives, coated abrasives, nonwoven abrasives, and abrasive brushes.

[0001] This application is a continuation-in-part of U.S. Ser. Nos. 09/922,526, 09/922,527, 09/922,528, and 09/922,530, filed Aug. 2, 2001, the disclosures of which are incorporated herein by reference.

FIELD OF THE INVENTION

[0002] This invention relates to alumina-zirconia materials.

[0003] Description of Related Art

[0004] Alumina-zirconia ceramic materials (including stabilized zirconias) such as alumina-toughened zirconia, zirconia-toughened alumina, alumina-zirconia eutectics are known to have very desirable properties such as high strength, toughness, hardness, high temperature creep resistance, and chemical inertness. It is also known to modify properties of alumina-zirconia materials by additions of metal oxides, nitrides, and carbides.

[0005] Such alumina-zirconia and alumina-zirconia-based ceramics have been fabricated into forms such as particles, coatings, fibers, and bulk materials. Known uses of such materials include fillers, abrasive particles, cutting tool inserts, grinding media, refractories, fibers, thermal-barrier, abrasion, and corrosion resistant coatings.

[0006] Methods for making known bulk alumina-zirconia and alumina-zirconia-based ceramics include powder coalescence (i.e., by sintering, hot pressing, HIPing, etc.) techniques, sol-gel processing, fusion, and plasma processing such as plasma spraying. Methods for making known alumina-zirconia and alumina-zirconia-based ceramics in particulate form include crushing the bulk materials and atomization techniques for making spherical particles. The form of the alumina-zirconia and alumina-zirconia-based in terms of being amorphous, crystalline, or a combination thereof, and for crystalline materials, the particular microstructure, may depend for a given composition, for example, on the processing method and processing conditions.

[0007] Forms of amorphous or partially amorphous alumina-zirconia made by fusion processing rapidly quenching a melt or other (such as atomization and plasma processing) are known. Formation of predominantly amorphous alumina-zirconia powders by spray pyrolysis of salts is also known.

[0008] Further, although many metal oxides can be obtained in an amorphous (including glassy) state by melting and rapidly quenching, most, because of the need for very high quench rates to provide amorphous material, tend to form crystalline material if the size of the material is too large. Hence many cannot be formed into bulk or complex shapes. Generally, such systems are very unstable against crystallization during subsequent reheating and therefore do not exhibit such properties as viscous flow.

[0009] On the other hand, glasses based on the conventional network forming oxides(e.g., silica and boria) are generally relatively stable against crystallization during reheating and, correspondingly, the “working” range where viscous flow occurs can readily be accessed. Formation of large articles from powders of known glass (e.g., silica and boria) via viscous sintering at temperatures above glass transition temperature is well known. For example, in the abrasive industry, grinding wheels are made using vitrified bond to secure abrasive particles together.

[0010] Although amorphous and crystalline forms of alumina-zirconia are known, new forms and/or alumina-zirconia compositions are desirable, particularly those that in are or can be used to make useful (bulk) articles or abrasive particles.

SUMMARY OF THE INVENTION

[0011] In one aspect, the present invention provides amorphous material comprising Al₂O₃ (in some embodiments preferably, at least 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, or even, at least 70 percent by weight Al₂O₃, based on the total weight of the amorphous material), ZrO₂ (in some embodiments preferably, at least 15, 20, 25, 30, 35, 40, or even, at least 45 percent by weight ZrO₂, based on the total weight of the amorphous material), and a metal oxide other than Al₂O₃ or ZrO₂ (e.g., Y₂O₃, REO, TiO₂, CaO, Cr₂O₃, MgO, NiO, CuO, and complex metal oxides thereof), wherein at least a portion of the metal oxide other than Al₂O₃ or ZrO₂ forms a distinct crystalline phase when the amorphous material is crystallized, wherein the amorphous material comprises at least 50 (in some embodiments preferably, at least 55, 60, 65, 70, 75, 80, 85, 90, or even 95)percent by weight collectively of the Al₂O₃ and the ZrO₂, based on the total weight of the amorphous material, wherein the amorphous material contains not more than 20 (in some embodiments, preferably not more than 15, 10, 5, 4, 3, 2, 1, or zero) percent by weight collectively As₂O₃, B₂O₃, GeO₂, P₂O₅, SiO₂, TeO₂, and V₂O₅, based on the total weight of the amorphous material, wherein the amorphous material has x, y, and z dimensions each perpendicular to each other, and wherein each of the x, y, and z dimensions is at least 25 micrometers (in some embodiments, preferably, at least 30 micrometers, 35 micrometers, 40 micrometers, 45 micrometers, 50 micrometers, 75 micrometers, 100 micrometers, 150 micrometers, 200 micrometers, 250 micrometers, 500 micrometers, 1000 micrometers, 2000 micrometers, 2500 micrometers, 1 mm, 5 mm, or even at least 10 mm).

[0012] A “distinct crystalline phase” is a crystalline phase (including a crystalline complex metal oxide) that is detectable by x-ray diffraction as opposed to a phase that is present in solid solution with another distinct crystalline phase. For example, it is well known that oxides such as Y₂O₃ or CeO₂ may be in solid solution with a crystalline ZrO₂ and serve as a phase stabilizer. The Y₂O₃ or CeO₂ in such instances is not a distinct crystalline phase.

[0013] The x, y, and z dimensions of a material are determined either visually or using microscopy, depending on the magnitude of the dimensions. The reported z dimension is, for example, the diameter of a sphere, the thickness of a coating, or the longest length of a prismatic shape.

[0014] In this application:

[0015] “amorphous material” refers to material derived from a melt and/or a vapor phase that lacks any long range crystal structure as determined by X-ray diffraction and/or has an exothermic peak corresponding to the crystallization of the amorphous material as determined by a DTA (differential thermal analysis) as determined by the test described herein entitled “Differential Thermal Analysis”;

[0016] “ceramic” includes amorphous material, glass, crystalline ceramic, glass-ceramic, and combinations thereof;

[0017] “complex metal oxide” refers to a metal oxide comprising two or more different metal elements and oxygen (e.g., CeAl₁₁O₈, Dy₃Al₅O₁₂, MgAl₂O₄, and Y₃Al₅O₁₂);

[0018] “complex Al₂O₃.metal oxide” refers to a complex metal oxide comprising, on a theoretical oxide basis, Al₂O₃ and one or more metal elements other than Al (e.g., CeAl₁₁O₁₈, Dy₃Al₅O₁₂, MgAl₂O₄, and Y₃Al₅O₁₂);

[0019] “complex Al₂O₃.Y₂O₃” refers to a complex metal oxide comprising, on a theoretical oxide basis, Al₂O₃ and Y₂O₃ (e.g., Y₃Al₅O₁₂);

[0020] “complex Al₂O₃.REO” refers to a complex metal oxide comprising, on a theoretical oxide basis, Al₂O₃ and rare earth oxide (e.g., CeAl₁₁O₁₈ and Dy₃Al₅O₁₂);

[0021] “glass” refers to amorphous material exhibiting a glass transition temperature;

[0022] “glass-ceramic” refers to ceramic comprising crystals formed by heat-treating amorphous material;

[0023] “T_(g)” refers to the glass transition temperature as determined by the test described herein entitled “Differential Thermal Analysis”;

[0024] “T_(x)” refers to the crystallization temperature as determined by the test described herein entitled “Differential Thermal Analysis”;

[0025] “rare earth oxides” refers to cerium oxide (e.g., CeO₂), dysprosium oxide (e.g., Dy₂O₃), erbium oxide (e.g., Er₂O₃), europium oxide (e.g., Eu₂O₃), gadolinium (e.g., Gd₂O₃), holmium oxide (e.g., Ho₂O₃), lanthanum oxide (e.g., La₂O₃), lutetium oxide (e.g., Lu₂O₃), neodymium oxide (e.g., Nd₂O₃), praseodymium oxide (e.g., Pr₆O₁₁), samarium oxide (e.g., Sm₂O₃), terbium (e.g., Tb₂O₃), thorium oxide (e.g., Th₄O₇), thulium (e.g., Tm₂O₃), and ytterbium oxide (e.g., Yb₂O₃), and combinations thereof; and

[0026] “REO” refers to rare earth oxide(s).

[0027] Further, it is understood herein that unless it is stated that a metal oxide (e.g., Al₂O₃, complex Al₂O₃.metal oxide, etc.) is crystalline, for example, in a glass-ceramic, it may be amorphous, crystalline, or portions amorphous and portions crystalline. For example 1f a glass-ceramic comprises Al₂O₃ and ZrO₂, the Al₂O₃ and ZrO₂ may each be in an amorphous state, crystalline state, or portions in an amorphous state and portions in a crystalline state, or even as a reaction product with another metal oxide(s) (e.g., unless it is stated that, for example, Al₂O₃ is present as crystalline Al₂O₃ or a specific crystalline phase of Al₂O₃ (e.g., alpha Al₂O₃), it may be present as crystalline Al₂O₃ and/or as part of one or more crystalline complex Al₂O₃.metal oxides.

[0028] Further, it is understood that glass-ceramics formed by heating amorphous material not exhibiting a T_(g) may not actually comprise glass, but rather may comprise the crystals and amorphous material that does not exhibiting a T_(g).

[0029] In one aspect, the present invention provides glass-ceramic comprising Al₂O₃ (in some embodiments preferably, at least 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, or even, at least 70 percent by weight Al₂O₃, based on the total weight of the glass-ceramic), ZrO₂ (in some embodiments preferably, at least 15, 20, 25, 30, 35, 40, or even, at least 45 percent by weight ZrO₂, based on the total weight of the glass-ceramic), and a metal oxide other than Al₂O₃ or ZrO₂ (e.g., Y₂O₃, REO, TiO₂, CaO, Cr₂O₃, MgO, NiO, CuO, and complex metal oxides thereof), wherein at least a portion of the metal oxide other than Al₂O₃ or ZrO₂ is present as at least one distinct crystalline phase, wherein the glass-ceramic comprises at least 50 (in some embodiments preferably, at least 55, 60, 65, 70, 75, 80, 85, 90, or even 95) percent by weight collectively of the Al₂O₃ and the ZrO₂, based on the total weight of the glass-ceramic, wherein the glass-ceramic contains not more than 20 (in some embodiments, preferably not more than 15, 10, 5, 4, 3, 2, 1, or zero) percent by weight collectively As₂O₃, B₂O₃, GeO₂, P₂O₅, SiO₂, TeO₂, and V₂O₅, based on the total weight of the glass-ceramic, wherein the glass-ceramic has x, y, and z dimensions each perpendicular to each other, and wherein each of the x, y, and z dimensions is at least 25 micrometers (in some embodiments, preferably, at least 30 micrometers, 35 micrometers, 40 micrometers, 45 micrometers, 50 micrometers, 75 micrometers, 100 micrometers, 150 micrometers, 200 micrometers, 250 micrometers, 500 micrometers, 1000 micrometers, 2000 micrometers, 2500 micrometers, 1 mm, 5 mm, or even at least 10 mm).

[0030] In some embodiments, the amorphous material may present in another material (e.g., particles comprising the amorphous material according to the present invention, ceramic comprising the amorphous material according to the present invention, etc.). Optionally, the amorphous material (including a glass) is heat-treated such that at least a portion of the amorphous material is converted to a glass-ceramic.

[0031] In one aspect, the present invention provides abrasive particles according to the present invention comprise a glass-ceramic. Some embodiments of abrasive particles according to the present invention comprise a glass-ceramic, wherein the glass-ceramic comprises Al₂O₃ (in some embodiments preferably, at least 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, or even, at least 70 percent by weight Al₂O₃, based on the total weight of the glass-ceramic), at least 15 (in some embodiments preferably, at least 20, 25, 30, 35, 40, or even, at least 45 percent by weight ZrO₂, based on the total weight of the glass-ceramic), and Y₂O₃ (in some embodiments preferably, at least 0.5 to 15%, more preferably 1 to 10 percent by weight Y₂O₃, based on the total weight of the glass-ceramic), wherein at least a portion of the Y₂O₃ is present as at least one distinct crystalline phase (e.g., crystalline Y₂O₃ and/or crystalline complex Y₂O₃.metal oxide).

[0032] Some embodiments of abrasive particles according to the present invention comprise a glass-ceramic, wherein the glass-ceramic comprises Al₂O₃ (in some embodiments preferably, at least 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, or even, at least 70 percent by weight Al₂O₃, based on the total weight of the glass-ceramic), at least 15 (in some embodiments preferably, at least 20, 25, 30, 35, 40,, or even, at least 45 percent by weight ZrO₂, based on the total weight of the glass-ceramic, and REO (in some embodiments preferably, at least 0.5 to 15%, more preferably 1 to 10 percent by weight REO, based on the total weight of the glass-ceramic), wherein at least a portion of the REO is present as at least one distinct crystalline phase (e.g., crystalline REO and/or crystalline complex REO.metal oxide).

[0033] Some embodiments of abrasive particles according to the present invention comprise a glass-ceramic, wherein the glass-ceramic comprises Al₂O₃ (in some embodiments preferably, at least 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, or even, at least 70 percent by weight Al₂O₃, based on the total weight of the amorphous material), at least 15 (in some embodiments preferably, at least 20, 25, 30, 35, 40, 45, or even, at least 45) percent by weight ZrO₂, based on the total weight of the glass-ceramic, and contains not more than 10 (in some embodiments, preferably not more than 5, 4, 3, 2, 1, or zero) percent by weight collectively As₂O₃, B₂O₃, GeO₂, P₂O₅, SiO₂, TeO₂, and V₂O₅, based on the total weight of the glass-ceramic, wherein the glass-ceramic has x, y, and z dimensions each perpendicular to each other, and wherein each of the x, y, and z dimensions is at least 25 micrometers.

[0034] Some embodiments of abrasive particles according to the present invention comprise a glass-ceramic, wherein the glass-ceramic comprises Al₂O₃ (in some embodiments preferably, at least 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, or even, at least 70 percent by weight Al₂O₃, based on the total weight of the glass-ceramic), ZrO₂ (in some embodiments preferably, at least 20, 25, 30, 35, 40, or even, at least 45 percent by weight ZrO₂, based on the total weight of the glass-ceramic), and a metal oxide other than Al₂O₃ or ZrO₂ (e.g., Y₂O₃, REO, TiO₂, CaO, Cr₂O₃, MgO, NiO, CuO, and complex metal oxides thereof), wherein at least a portion of the metal oxide other than Al₂O₃ or ZrO₂ is present as at least one distinct crystalline phase, wherein the glass-ceramic collectively comprises at least 50 (in some embodiments preferably, at least 55, 60, 65, 70, 75, 80, 85, 90, or even 95) percent by weight collectively of the Al₂O₃ and the ZrO₂, based on the total weight of the glass-ceramic, wherein the glass-ceramic contains not more than 20 (in some embodiments, preferably not more than 15, 10, 5, 4, 3, 2, 1, or zero) percent by weight collectively As₂O₃, B₂O₃, GeO₂, P₂O₅, SiO₂, TeO₂, and V₂O₅, based on the total weight of the glass-ceramic.

[0035] In another aspect, the present invention provides a method for making abrasive particles, the method comprising:

[0036] heat-treating amorphous material (including a glass) such that at least a portion of the amorphous material is converted to a glass-ceramic; and

[0037] crushing the glass-ceramic to provide abrasive particles comprising the glass-ceramic.

[0038] The abrasive particles can be incorporated into an abrasive article, or used in loose form. Abrasive articles according to the present invention comprise binder and a plurality of abrasive particles, wherein at least a portion of the abrasive particles are the abrasive particles according to the present invention. Exemplary abrasive products include coated abrasive articles, bonded abrasive articles (e.g., wheels), non-woven abrasive articles, and abrasive brushes. Coated abrasive articles typically comprise a backing having first and second, opposed major surfaces, and wherein the binder and the plurality of abrasive particles form an abrasive layer on at least a portion of the first major surface.

[0039] In some embodiments, preferably, at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50 55, 60, 65, 70, 75, 80, 85, 90, 95, or even 100 percent by weight of the abrasive particles in an abrasive article are the abrasive particles according to the present invention, based on the total weight of the abrasive particles in the abrasive article.

[0040] Abrasive particles are usually graded to a given particle size distribution before use. Such distributions typically have a range of particle sizes, from coarse particles fine particles. In the abrasive art this range is sometimes referred to as a “coarse”, “control” and “fine” fractions. Abrasive particles graded according to industry accepted grading standards specify the particle size distribution for each nominal grade within numerical limits. Such industry accepted grading standards (i.e., specified nominal grades) include those known as the American National Standards Institute, Inc. (ANSI) standards, Federation of European Producers of Abrasive Products (FEPA) standards, and Japanese Industrial Standard (JIS) standards. In one aspect, the present invention provides a plurality of abrasive particles having a specified nominal grade, wherein at least a portion of the plurality of abrasive particles are abrasive particles according to the present invention. In some embodiments, preferably, at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50 55, 60, 65, 70, 75, 80, 85, 90, 95, or even 100 percent by weight of the plurality of abrasive particles are the abrasive particles according to the present invention, based on the total weight of the plurality of abrasive particles.

[0041] In another aspect, the present invention provides a method for making abrasive particles according to the present invention, the method comprising heat-treating particles comprising the amorphous material (including glass) such that at least a portion of the amorphous material converts to a glass-ceramic provide the abrasive particles comprising the glass-ceramic. Typically, the abrasive particles comprising the glass-ceramic are graded after heat-treating to provide a plurality of abrasive particles having a specified nominal grade, wherein at least a portion of the plurality of abrasive particles is a plurality of the abrasive particles comprising the glass-ceramic. Optionally, prior to the heat-treating the particles the amorphous material, a plurality of particles having a specified nominal grade is provided, wherein at least a portion of the particles is a plurality of the particles comprising the amorphous material to be heat-treated, and wherein the heat-treating is conducted such that a plurality of abrasive particles having a specified nominal grade is provided, wherein at least a portion of the abrasive particles is a plurality of the abrasive particles comprising the glass-ceramic.

[0042] In another aspect, the present invention provides a method for making abrasive particles according to the present invention, the method comprising heat-treating particles comprising the amorphous material such that at least a portion of the amorphous material converts to a glass-ceramic to provide the abrasive particles comprising the glass-ceramic. Typically, the abrasive particles comprising the glass-ceramic are graded after heat-treating to provide a plurality of abrasive particles having a specified nominal grade, wherein at least a portion of the plurality of abrasive particles is a plurality of the abrasive particles comprising the glass-ceramic. Optionally, prior to the heat-treating the particles comprising the amorphous material, a plurality of particles having a specified nominal grade is provided, wherein at least a portion of the particles is a plurality of the particles comprising the amorphous material to be heat-treated, and wherein the heat-treating is conducted such that a plurality of abrasive particles having a specified nominal grade is provided, wherein at least a portion of the abrasive particles is a plurality of the abrasive particles comprising the glass-ceramic.

[0043] Amorphous materials and glass-ceramics according to the present invention can be made, formed as, or converted into particles (e.g., glass beads (e.g., beads having diameters of at least 1 micrometers, 5 micrometers, 10 micrometers, 25 micrometers, 50 micrometers, 100 micrometers, 150 micrometers, 250 micrometers, 500 micrometers, 750 micrometers, 1 mm, 5 mm, or even at least 10 mm)), articles (e.g., plates), fibers, particles, and coatings (e.g., thin coatings). Amorphous materials and/or glass-ceramic particles and fibers are useful, for example, as thermal insulation, filler, or reinforcing material in composites (e.g., ceramic, metal, or polymeric matrix composites). The thin coatings can be useful, for example, as protective coatings in applications involving wear, as well as for thermal management. Examples of articles according of the present invention include kitchenware (e.g., plates), dental brackets, and reinforcing fibers, cutting tool inserts, abrasive materials, and structural components of gas engines, (e.g., valves and bearings). Other articles include those having a protective coating of ceramic on the outer surface of a body or other substrate.

BRIEF DESCRIPTION OF THE DRAWING

[0044]FIG. 1 is a fragmentary cross-sectional schematic view of a coated abrasive article including abrasive particles according to the present invention;

[0045]FIG. 2 is a perspective view of a bonded abrasive article including abrasive particles according to the present invention;

[0046]FIG. 3 is an enlarged schematic view of a nonwoven abrasive article including abrasive particles according to the present invention;

[0047]FIG. 4 is a Scanning Electron Micrograph (SEM) of fractured surface of material prepared in Example 1;

[0048]FIG. 5 is a Scanning Electron Micrograph (SEM) of fractured surface of material prepared in Example 3;

[0049]FIG. 6 is a DTA curve of Example 22 material;

[0050] FIGS. 7-8 are DTA curves of materials prepared in Examples 23 and 24, respectively;

[0051]FIG. 9 is an optical photomicrograph of a section of Example 32 hot-pressed material;

[0052]FIG. 10 is an SEM photomicrograph of a polished cross-section of heat-treated Example 32 material;

[0053]FIG. 11 is an DTA curve of Example 32 material; and

[0054]FIG. 12 is an SEM photomicrograph of a polished cross-section of Example 52 material.

DETAILED DESCRIPTION

[0055] Some embodiments of amorphous materials (including glasses), glass-ceramics, abrasive particles according to the present invention comprising the glass-ceramics, amorphous materials (including glasses) for making the glass-ceramics, abrasive particles, etc. include those comprising Al₂O₃ (in some embodiments preferably, at least 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, or even at least 70 percent by weight Al₂O₃, based on the total weight of the amorphous material or glass-ceramic, as applicable), ZrO₂ (in some embodiments preferably, at least 15, 20, 25, 30, 35, 40, or even at least 45 percent by weight ZrO₂, based on the total weight of the amorphous material or glass-ceramic, as applicable), and a metal oxide other than Al₂O₃ or ZrO₂ (e.g., Y₂O₃, REO, MgO, TiO₂, NiO, CaO, Cr₂O₃, CuO and complex metal oxides thereof), wherein at least a portion of the metal oxide other than Al₂O₃ or ZrO₂ forms a distinct crystalline phase during heat-treating, wherein the amorphous material or glass-ceramic, as applicable, comprises at least 50 (in some embodiments preferably, at least 55, 60, 65, 70, 75, 80, 85, 90, or even 95) percent by weight collectively of the Al₂O₃ and the ZrO₂, based on the total weight of the amorphous material or glass-ceramic, as applicable, wherein the amorphous material or glass-ceramic, as applicable, contains not more than 20 (in some embodiments, preferably not more than 15, 10, 5, 4, 3, 2, 1, or zero) percent by weight collectively As₂O₃, B₂O₃, GeO₂, P₂O₅, SiO₂, TeO₂, and V₂O₅, based on the total weight of the amorphous material or glass-ceramic, as applicable.

[0056] Some embodiments of amorphous materials (including glasses), glass-ceramics, abrasive particles according to the present invention comprising the glass-ceramics, amorphous materials (including glasses) for making the glass-ceramics, abrasive particles, etc. include those comprising Al₂O₃ (in some embodiments preferably, at least 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, or even at least 70 percent by weight Al₂O₃, based on the total weight of the glass-ceramic), at least 15 (in some embodiments preferably, at least 20, 25, 30, 35, 40, or even at least 45) percent by weight ZrO₂, based on the total weight of the amorphous material or glass-ceramic, as applicable) percent by weight ZrO₂, based on the total weight of the amorphous material or glass-ceramic, as applicable, and Y₂O₃ (in some embodiments preferably, at least 0.5 to 15%, more preferably 1 to 10 percent by weight Y₂O₃, based on the total weight of the amorphous material or glass-ceramic, as applicable), wherein at least a portion of the Y₂O₃ forms a distinct crystalline phase during heat-treating.

[0057] Some embodiments of amorphous materials (including glasses), glass-ceramics, abrasive particles according to the present invention comprising the glass-ceramics, amorphous materials (including glasses) for making the glass-ceramics, abrasive particles, etc. include those comprising Al₂O₃ (in some embodiments preferably, at least 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, or even at least 70 percent by weight Al₂O₃, based on the total weight of the glass-ceramic), at least 15 (in some embodiments preferably, at least 20, 25, 30, 35, 40, or even at least 45) percent by weight ZrO₂, based on the total weight of the amorphous material or glass-ceramic, as applicable) percent by weight ZrO₂, based on the total weight of the amorphous material or glass-ceramic, as applicable, and Y₂O₃ (in some embodiments preferably, at least 0.5 to 15%, more preferably 1 to 10 percent by weight Y₂O₃, based on the total weight of the amorphous material or glass-ceramic, as applicable), wherein at least a portion of the Y₂O₃ forms a distinct crystalline phase during heat-treating.

[0058] Some embodiments of amorphous materials (including glasses), glass-ceramics, abrasive particles according to the present invention comprising the glass-ceramics, amorphous materials (including glasses) for making the glass-ceramics, abrasive particles, etc. include those comprising Al₂O₃ (in some embodiments preferably, at least 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, or even at least 70 percent by weight Al₂O₃, based on the total weight of the amorphous material or glass-ceramic, as applicable), at least 15 (in some embodiments preferably, at least 20, 25, 30, 35, 40, or even at least 45) percent by weight ZrO₂, based on the total weight of the amorphous material or glass-ceramic, as applicable, and contains not more than 10 (in some embodiments, preferably not more than 5, 4, 3, 2, 1, or zero) percent by weight collectively As₂O₃, B₂O₃, GeO₂, P₂O₅, SiO₂, TeO₂, and V₂O₅, based on the total weight of the amorphous material or glass-ceramic, as applicable, wherein the amorphous material or glass-ceramic, as applicable, has x, y, and z dimensions each perpendicular to each other, and wherein each of the x, y, and z dimensions is at least 25 micrometers (in some embodiments, preferably, at least 30 micrometers, 35 micrometers, 40 micrometers, 45 micrometers, 50 micrometers, 75 micrometers, 100 micrometers, 150 micrometers, 200 micrometers, 250 micrometers, 500 micrometers, 1000 micrometers, 2000 micrometers, 2500 micrometers, 1 mm, 5 mm, or even at least 10 mm).

[0059] Some embodiments of amorphous materials (including glasses), glass-ceramics, abrasive particles according to the present invention comprising the glass-ceramics, amorphous materials (including glasses) for making the glass-ceramics, abrasive particles, etc. include those comprising Al₂O₃ (in some embodiments preferably, at least 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, or even at least 70 percent by weight Al₂O₃, based on the total weight of the amorphous material or glass-ceramic, as applicable), ZrO₂ (in some embodiments preferably, at least 20, 25, 30, 35, 40, or even at least 45 percent by weight ZrO₂, based on the total weight of the amorphous material or glass-ceramic, as applicable), and a metal oxide other than Al₂O₃ or ZrO₂ (e.g., Y₂O₃, REO, MgO, TiO₂, NiO, CaO, Cr₂O₃, CuO and complex metal oxides thereof), wherein at least a portion of the metal oxide other than Al₂O₃ or ZrO₂ forms a distinct crystalline phase during heat-treating, wherein the amorphous material or glass-ceramic, as applicable, comprises at least 50 percent by weight collectively of the Al₂O₃ and the ZrO₂, based on the total weight of the amorphous material or glass-ceramic, as applicable, wherein the amorphous material or glass-ceramic, as applicable, contains not more than 20 (in some embodiments, preferably not more than 15, 10, 5, 4, 3, 2, 1, or zero) percent by weight collectively As₂O₃, B₂O₃, GeO₂, P₂O₅, SiO₂, TeO₂, and V₂O₅, based on the total weight of the amorphous material or glass-ceramic, as applicable, wherein the amorphous material or glass-ceramic, as applicable, has x, y, and z dimensions each perpendicular to each other, wherein each of the x, y, and z dimensions is at least 25 micrometers (in some embodiments, preferably, at least 30 micrometers, 35 micrometers, 40 micrometers, 45 micrometers, 50 micrometers, 75 micrometers, 100 micrometers, 150 micrometers, 200 micrometers, 250 micrometers, 500 micrometers, 1000 micrometers, 2000 micrometers, 2500 micrometers, 1 mm, 5 mm, or even at least 10 mm).

[0060] Optionally, if embodiments of amorphous materials (including glasses), glass-ceramics, abrasive particles according to the present invention comprising the glass-ceramics, amorphous materials (including glasses) for making the glass-ceramics, abrasive particles, etc. described herein do not already specify, embodiments of the amorphous materials, glass-ceramics, etc. may preferably contain not more than 10 (in some embodiments preferably, less than 5, 4, 3, 2, 1, or even zero) percent by weight collectively As₂O₃, B₂O₃, GeO₂, P₂O₅, SiO₂, TeO₂, and V₂O₅, based on the total weight of the ceramics, abrasive particles, etc. described herein do not already specify, embodiments of the amorphous materials or glass-ceramic, as applicable.

[0061] Optionally, if embodiments of amorphous materials (including glasses), glass-ceramics, abrasive particles according to the present invention comprising the glass-ceramics, amorphous materials (including glasses) for making the glass-ceramics, abrasive particles, etc. described herein do not already specify, embodiments of the amorphous material or glass-ceramic, as applicable, may preferably contain not more than 15, 10, 5, 4, 3, 2, 1, or even zero percent by weight SiO₂, based on the total weight of the amorphous material or glass-ceramic, as applicable.

[0062] Optionally, if embodiments of amorphous materials (including glasses), glass-ceramics, abrasive particles according to the present invention comprising the glass-ceramics, amorphous materials (including glasses) for making the glass-ceramics, abrasive particles, etc. described herein do not already specify, embodiments of the amorphous material or glass-ceramic, as applicable, preferably contain not more than 10, 5, 4, 3, 2, 1, or even zero percent by weight B₂O₃ and not more than 10, 5, 4, 3, 2, 1, or even zero percent by weight B₂O₃, based on the total weight of the amorphous material or glass-ceramic, as applicable.

[0063] Optionally, if embodiments of amorphous materials (including glasses), glass-ceramics, abrasive particles according to the present invention comprising the glass-ceramics, amorphous materials (including glasses) for making the glass-ceramics, abrasive particles, etc. described herein do not already specify, embodiments of the amorphous material or glass-ceramic, as applicable, preferably contain not more than 10, 5, 4, 3, 2, 1, or even zero percent by weight collectively SiO₂, B₂O₃, and P₂O₅, based on the total weight of the amorphous material or glass-ceramic, as applicable.

[0064] Optionally, if embodiments of amorphous materials (including glasses), glass-ceramics, abrasive particles according to the present invention comprising the glass-ceramics, amorphous materials (including glasses) for making the glass-ceramics, abrasive particles, etc. described herein do not already specify, at least a portion of the amorphous material has x, y, and z dimensions each perpendicular to each other, and wherein each of the x, y, and z dimensions is at least 10 micrometers, at least 25 micrometers, at least 30 micrometers, 35 micrometers, 40 micrometers, 45 micrometers, 50 micrometers, 75 micrometers, 100 micrometers, 150 micrometers, 200 micrometers, 250 micrometers, 500 micrometers, 1000 micrometers, 2000 micrometers, 2500 micrometers, 1 mm, 5 mm, or even at least 10 mm.

[0065] Optionally, if embodiments of amorphous materials (including glasses), glass-ceramics, abrasive particles according to the present invention comprising the glass-ceramics, amorphous materials (including glasses) for making the glass-ceramics, abrasive particles, etc. described herein comprise at least 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, or even at least 70 percent by weight Al₂O₃, based on the total weight of the amorphous material or glass-ceramic, as applicable.

[0066] In some embodiments, amorphous materials (including glasses), glass-ceramics, abrasive particles according to the present invention comprising the glass-ceramics, amorphous materials (including glasses) for making the glass-ceramics, abrasive particles, etc. preferably comprise Al₂O₃ in a range of about 55 to about 65 percent by weight to a range of about 45 to about 35 percent by weight ZrO₂, based on the total Al₂O₃ and ZrO₂ content of the amorphous material or glass-ceramic, as applicable. In some embodiments, amorphous materials (including glasses), glass-ceramics, abrasive particles according to the present invention comprising the glass-ceramics, amorphous materials (including glasses) for making the glass-ceramics, abrasive particles, etc. preferably comprise about 60 percent by weight Al₂O₃ and about 40 percent by weight ZrO₂, based on the total Al₂O₃ and ZrO₂ content of the amorphous material or glass-ceramic, as applicable.

[0067] In some embodiments, amorphous materials (including glasses), glass-ceramics, abrasive particles according to the present invention comprising the glass-ceramics, amorphous materials (including glasses) for making the glass-ceramics, abrasive particles, etc. the weight ratio of Al₂O₃ to ZrO₂ is preferably in a range from 1:10 to 10:1, more preferably, about 3:2.

[0068] Amorphous materials (e.g., glasses), ceramics comprising the amorphous material, particles comprising the amorphous material, etc. can be made, for example, by heating (including in a flame) the appropriate metal oxide sources to form a melt, desirably a homogenous melt, and then rapidly cooling the melt to provide amorphous material. Embodiments of amorphous materials can be made, for example, by melting the metal oxide sources in any suitable furnace (e.g., an inductive heated furnace, a gas-fired furnace, or an electrical furnace), or, for example, in a plasma. The resulting melt is cooled (e.g., discharging the melt into a cooling media (e.g., high velocity air jets, liquids, metal plates (including chilled metal plates), metal rolls (including chilled metal rolls), metal balls (including chilled metal balls), and the like)).

[0069] Embodiments of amorphous material can be made utilizing flame fusion as disclosed, for example, in U.S. Pat. No. 6,254,981 (Castle), the disclosure of which is incorporated herein by reference. In this method, the metal oxide sources materials are fed (e.g., in the form of particles, sometimes referred to as “feed particles”) directly into a burner (e.g., a methane-air burner, an acetylene-oxygen burner, a hydrogen-oxygen burner, and like), and then quenched, for example, in water, cooling oil, air, or the like. Feed particles can be formed, for example, by grinding, agglomerating (e.g., spray-drying), melting, or sintering the metal oxide sources. The size of feed particles fed into the flame generally determine the size of the resulting amorphous material comprising particles.

[0070] Embodiments of amorphous materials can also be obtained by other techniques, such as: laser spin melt with free fall cooling, Taylor wire technique, plasmatron technique, hammer and anvil technique, centrifugal quenching, air gun splat cooling, single roller and twin roller quenching, roller-plate quenching and pendant drop melt extraction (see, e.g., Rapid Solidification of Ceramics, Brockway et. al, Metals And Ceramics Information Center, A Department of Defense Information Analysis Center, Columbus, Ohio, January, 1984, the disclosure of which is incorporated here as a reference). Embodiments of amorphous materials may also be obtained by other techniques, such as: thermal (including flame or laser or plasma-assisted) pyrolysis of suitable precursors, physical vapor synthesis (PVS) of metal precursors and mechanochemical processing.

[0071] Useful amorphous material formulations include those at or near a eutectic composition(s) (e.g., binary and ternary eutectic compositions). In addition to compositions disclosed herein, other compositions, including quaternary and other higher order eutectic compositions, may be apparent to those skilled in the art after reviewing the present disclosure.

[0072] Sources, including commercial sources, of (on a theoretical oxide basis) Al₂O₃ include bauxite (including both natural occurring bauxite and synthetically produced bauxite), calcined bauxite, hydrated aluminas (e.g., boehmite, and gibbsite), aluminum, Bayer process alumina, aluminum ore, gamma alumina, alpha alumina, aluminum salts, aluminum nitrates, and combinations thereof. The Al₂O₃ source may contain, or only provide, Al₂O₃. Alternatively, the Al₂O₃ source may contain, or provide Al₂O₃, as well as one or more metal oxides other than Al₂O₃ (including materials of or containing complex Al₂O₃.metal oxides (e.g., Dy₃Al₅O₁₂, Y₃Al₅O₁₂, CeAl₁₁O₁₈, etc.)).

[0073] Sources, including commercial sources, of (on a theoretical oxide basis) ZrO₂ include zirconium oxide powders, zircon sand, zirconium, zirconium-containing ores, and zirconium salts (e.g., zirconium carbonates, acetates, nitrates, chlorides, hydroxides, and combinations thereof). In addition, or alternatively, the ZrO₂ source may contain, or provide ZrO₂, as well as other metal oxides such as hafnia. Sources, including commercial sources, of (on a theoretical oxide basis) HfO₂ include hafnium oxide powders, hafnium, hafnium-containing ores, and hafnium salts. In addition, or alternatively, the HfO₂ source may contain, or provide HfO₂, as well as other metal oxides such as ZrO₂. It may be desirable to add metal oxides (e.g., Y₂O₃, TiO₂, CaO, and MgO) that are known to stabilize tetragonal/cubic form of ZrO₂.

[0074] Sources, including commercial sources, of rare earth oxides include rare earth oxide powders, rare earth metals, rare earth-containing ores (e.g., bastnasite and monazite), rare earth salts, rare earth nitrates, and rare earth carbonates. The rare earth oxide(s) source may contain, or only provide, rare earth oxide(s). Alternatively, the rare earth oxide(s) source may contain, or provide rare earth oxide(s), as well as one or more metal oxides other than rare earth oxide(s) (including materials of or containing complex rare earth oxide.other metal oxides (e.g., Dy₃Al₅O₁₂, CeAl₁₁O₁₈, etc.)).

[0075] Sources, including commercial sources, of (on a theoretical oxide basis) Y₂O₃ include yttrium oxide powders, yttrium, yttrium-containing ores, and yttrium salts (e.g., yttrium carbonates, nitrates, chlorides, hydroxides, and combinations thereof). The Y₂O₃ source may contain, or only provide, Y₂O₃. Alternatively, the Y₂O₃ source may contain, or provide Y₂O₃, as well as one or more metal oxides other than Y₂O₃ (including materials of or containing complex Y₂O₃.metal oxides (e.g., Y₃Al₅O₁₂)).

[0076] Other useful metal oxide may also include, on a theoretical oxide basis, BaO, CaO, Cr₂O₃, CoO, Fe₂O₃, GeO₂, Li₂O, MgO, MnO, NiO, Na₂O, Sc₂O₃, SrO, TiO₂, ZnO, and combinations thereof. Sources, including commercial sources, include the oxides themselves, complex oxides, ores, carbonates, acetates, nitrates, chlorides, hydroxides, etc. These metal oxides are added to modify a physical property of the resulting abrasive particles and/or improve processing. These metal oxides are typically are added anywhere from 0 to 50% by weight, in some embodiments preferably 0 to 25% by weight and more preferably 0 to 50% by weight of the glass-ceramic depending, for example, upon the desired property.

[0077] In some embodiments, it may be advantageous for at least a portion of a metal oxide source (in some embodiments, preferably, 10 15, 20, 25, 30, 35, 40, 45, or even at least 50 percent by weight) to be obtained by adding particulate, metallic material comprising at least one of a metal (e.g., Al, Ca, Cu, Cr, Fe, Li, Mg, Ni, Ag, Ti, Zr, and combinations thereof), M, that has a negative enthalpy of oxide formation or an alloy thereof to the melt, or otherwise metal them with the other raw materials. Although not wanting to be bound by theory, it is believed that the heat resulting from the exothermic reaction associated with the oxidation of the metal is beneficial in the formation of a homogeneous melt and resulting amorphous material. For example, it is believed that the additional heat generated by the oxidation reaction within the raw material eliminates or minimizes insufficient heat transfer, and hence facilitates formation and homogeneity of the melt, particularly when forming amorphous particles with x, y, and z dimensions over 150 micrometers. It is also believed that the availability of the additional heat aids in driving various chemical reactions and physical processes (e.g., densification, and spherodization) to completion. Further, it is believed for some embodiments, the presence of the additional heat generated by the oxidation reaction actually enables the formation of a melt, which otherwise is difficult or otherwise not practical due to high melting point of the materials. Further, the presence of the additional heat generated by the oxidation reaction actually enables the formation of amorphous material that otherwise could not be made, or could not be made in the desired size range. Another advantage of the invention include, in forming the amorphous materials, that many of the chemical and physical processes such as melting, densification and spherodizing can be achieved in a short time, so that very high quench rates be can achieved. For additional details, see copending application having U.S. Ser. No. ______ (Attorney Docket No. 56931US007), filed the same date as the instant application, the disclosure of which is incorporated herein by reference.

[0078] The particular selection of metal oxide sources and other additives for making ceramics according to the present invention typically takes into account, for example, the desired composition and microstructure of the resulting ceramics, the desired degree of crystallinity, if any, the desired physical properties (e.g., hardness or toughness) of the resulting ceramics, avoiding or minimizing the presence of undesirable impurities, the desired characteristics of the resulting ceramics, and/or the particular process (including equipment and any purification of the raw materials before and/or during fusion and/or solidification) being used to prepare the ceramics.

[0079] The addition of certain metal oxides may alter the properties and/or crystalline structure or microstructure of a glass-ceramic according to the present invention, as well as the processing of the raw materials and intermediates in making the glass-ceramic. For example, oxide additions such as MgO, CaO, Li₂O, and Na₂O have been observed to alter both the T_(g) (for a glass) and T_(x) (wherein T_(x) is the crystallization temperature) of amorphous material. Although not wishing to be bound by theory, it is believed that such additions influence glass formation. Further, for example, such oxide additions may decrease the melting temperature of the overall system (i.e., drive the system toward lower melting eutectic), and ease of amorphous material-formation. Complex eutectics in multi component systems (quaternary, etc.) may result in better amorphous material-forming ability. The viscosity of the liquid melt and viscosity of the glass in its' “working” range may also be affected by the addition of certain metal oxides such as MgO, CaO, Li₂O, and Na₂O. It is also within the scope of the present invention to incorporate at least one of halogens (e.g., fluorine and chlorine), or chalcogenides (e.g., sulfides, selenides, and tellurides) into the amorphous materials, and the glass-ceramics made there from.

[0080] Crystallization of the amorphous material and ceramic comprising the amorphous material may also be affected by the additions of certain materials. For example, certain metals, metal oxides (e.g., titanates and zirconates), and fluorides, for example, may act as nucleation agents resulting in beneficial heterogeneous nucleation of crystals. Also, addition of some oxides may change nature of metastable phases devitrifying from the amorphous material upon reheating.

[0081] The particular selection of metal oxide sources and other additives for making ceramics according to the present invention typically takes into account, for example, the desired composition and microstructure of the resulting ceramics, the desired degree of crystallinity, if any, the desired physical properties (e.g., hardness or toughness) of the resulting ceramics, avoiding or minimizing the presence of undesirable impurities, the desired characteristics of the resulting ceramics, and/or the particular process (including equipment and any purification of the raw materials before and/or during fusion and/or solidification) being used to prepare the ceramics.

[0082] The metal oxide sources and other additives can be in any form suitable to the process and equipment being used to make the amorphous materials according to the present invention, the glass-ceramics according to the present invention, etc. The raw materials can be melted and quenched using techniques and equipment known in the art for making oxide amorphous materials and amorphous metals. Desirable cooling rates include those of 50 K/s and greater. Cooling techniques known in the art include roll-chilling. Roll-chilling can be carried out, for example, by melting the metal oxide sources at a temperature typically 20-200° C. higher than the melting point, and cooling/quenching the melt by spraying it under high pressure (e.g., using a gas such as air, argon, nitrogen or the like) onto a high-speed rotary roll(s). Typically, the rolls are made of metal and are water cooled. Metal book molds may also be useful for cooling/quenching the melt.

[0083] Other techniques for forming melts, cooling/quenching melts, and/or otherwise forming amorphous material include vapor phase quenching, melt-extraction, plasma spraying, and gas or centrifugal atomization. Vapor phase quenching can be carried out, for example, by sputtering, wherein the metal alloys or metal oxide sources are formed into a sputtering target(s) which are used. The target is fixed at a predetermined position in a sputtering apparatus, and a substrate(s) to be coated is placed at a position opposing the target(s). Typical pressures of 10⁻³ torr of oxygen gas and Ar gas, discharge is generated between the target(s) and a substrate(s), and Ar or oxygen ions collide against the target to start reaction sputtering, thereby depositing a film of composition on the substrate. For additional details regarding plasma spraying, see, for example, copending application having U.S. Ser. No. ______ (Attorney Docket No. 57980US002), filed the same date as the instant application, the disclosure of which is incorporated herein by reference.

[0084] Gas atomization involves melting feed particles to convert them to melt. A thin stream of such melt is atomized through contact with a disruptive air jet (i.e., the stream is divided into fine droplets). The resulting substantially discrete, generally ellipsoidal amorphous material comprising particles (e.g., beads) are then recovered. Examples of bead sizes include those having a diameter in a range of about 5 micrometers to about 3 mm. Melt-extraction can be carried out, for example, as disclosed in U.S. Pat. No. 5,605,870 (Strom-Olsen et al.), the disclosure of which is incorporated herein by reference. Containerless glass forming techniques utilizing laser beam heating as disclosed, for example, in PCT application having Publication No. WO 01/27046 Al, published Apr. 4, 2001, the disclosure of which is incorporated herein by reference, may also be useful in making materials according to the present invention.

[0085] The cooling rate is believed to affect the properties of the quenched amorphous material. For instance, glass transition temperature, density and other properties of glass typically change with cooling rates.

[0086] Typically, it is preferred that the bulk material comprises at least 50, 60, 75, 80, 85, 90, 95, 98, 99, or even 100 percent by weight of the amorphous material.

[0087] Rapid cooling may also be conducted under controlled atmospheres, such as a reducing, neutral, or oxidizing environment to maintain and/or influence the desired oxidation states, etc. during cooling. The atmosphere can also influence amorphous material formation by influencing crystallization kinetics from undercooled liquid. For example, larger undercooling of Al₂O₃ melts without crystallization has been reported in argon atmosphere as compared to that in air.

[0088] The microstructure or phase composition (glassy/amorphous/crystalline) of a material can be determined in a number of ways. Various information can be obtained using optical microscopy, electron microscopy, differential thermal analysis (DTA), and x-ray diffraction (XRD), for example.

[0089] Using optical microscopy, amorphous material is typically predominantly transparent due to the lack of light scattering centers such as crystal boundaries, while crystalline material shows a crystalline structure and is opaque due to light scattering effects.

[0090] A percent amorphous yield can be calculated for beads using a −100+120 mesh size fraction (i.e., the fraction collected between 150-micrometer opening size and 125-micrometer opening size screens). The measurements are done in the following manner. A single layer of beads is spread out upon a glass slide. The beads are observed using an optical microscope. Using the crosshairs in the optical microscope eyepiece as a guide, beads that lay along a straight line are counted either amorphous or crystalline depending on their optical clarity. A total of 500 beads are counted and a percent amorphous yield is determined by the amount of amorphous beads divided by total beads counted.

[0091] Using DTA, the material is classified as amorphous if the corresponding DTA trace of the material contains an exothermic crystallization event (T_(x)). If the same trace also contains an endothermic event (T_(g)) at a temperature lower than T_(x) it is considered to consist of a glass phase. If the DTA trace of the material contains no such events, it is considered to contain crystalline phases.

[0092] Differential thermal analysis (DTA) can be conducted using the following method. DTA runs can be made (using an instrument such as that obtained from Netzsch Instruments, Selb, Germany under the trade designation “NETZSCH STA 409 DTA/TGA”) using a −140+170 mesh size fraction (i.e., the fraction collected between 105-micrometer opening size and 90-micrometer opening size screens). An amount of each screened sample (typically about 400 milligrams (mg)) is placed in a 100-microliter Al₂O₃ sample holder. Each sample is heated in static air at a rate of 10° C./minute from room temperature (about 25° C.) to 1100° C.

[0093] Using powder x-ray diffraction, XRD, (using an x-ray diffractometer such as that obtained under the trade designation “PHILLIPS XRG 3100” from Phillips, Mahwah, N.J., with copper K α1 radiation of 1.54050 Angstrom) the phases present in a material can be determined by comparing the peaks present in the XRD trace of the crystallized material to XRD patterns of crystalline phases provided in JCPDS (Joint Committee on Powder Diffraction Standards) databases, published by International Center for Diffraction Data. Furthermore, an XRD can be used qualitatively to determine types of phases. The presence of a broad diffused intensity peak is taken as an indication of the amorphous nature of a material. The existence of both a broad peak and well-defined peaks is taken as an indication of existence of crystalline matter within an amorphous matrix.

[0094] The initially formed amorphous material or ceramic (including glass prior to crystallization) may be larger in size than that desired. The amorphous material or ceramic can be converted into smaller pieces using crushing and/or comminuting techniques known in the art, including roll crushing, canary milling, jaw crushing, hammer milling, ball milling, jet milling, impact crushing, and the like. In some instances, it is desired to have two or multiple crushing steps. For example, after the ceramic is formed (solidified), it may be in the form of larger than desired. The first crushing step may involve crushing these relatively large masses or “chunks” to form smaller pieces. This crushing of these chunks may be accomplished with a hammer mill, impact crusher or jaw crusher. These smaller pieces may then be subsequently crushed to produce the desired particle size distribution. In order to produce the desired particle size distribution (sometimes referred to as grit size or grade), it may be necessary to perform multiple crushing steps. In general the crushing conditions are optimized to achieve the desired particle shape(s) and particle size distribution. Resulting particles that are of the desired size may be recrushed if they are too large, or “recycled” and used as a raw material for re-melting if they are too small.

[0095] The shape of the ceramic (including glass prior to crystallization) may depend, for example, on the composition and/or microstructure of the ceramic, the geometry in which it was cooled, and the manner in which the ceramic is crushed (i.e., the crushing technique used). In general, where a “blocky” shape is preferred, more energy may be employed to achieve this shape. Conversely, where a “sharp” shape is preferred, less energy may be employed to achieve this shape. The crushing technique may also be changed to achieve different desired shapes. The resulting particle may have an average aspect ratio ranging from 1:1 to 5:1, typically 1.25:1 to 3:1 and preferably 1.5:1 to 2.5:1.

[0096] It is also within the scope of the present invention, for example, to directly form ceramic (including glass prior to crystallization) may in desired shapes. For example, ceramic (including glass prior to crystallization) may be formed (including molded) by pouring or forming the melt into a mold.

[0097] It is also within the scope of the present invention, for example, to fabricate the ceramic (including glass prior to crystallization) by coalescing. This coalescing step in essence forms a larger sized body from two or more smaller particles. For example, amorphous material comprising particles (obtained, for example, by crushing) (including beads and microspheres), fibers, etc. may formed into a larger particle size. For example, ceramic (including glass prior to crystallization), may also be provided by heating, for example, particles comprising the amorphous material, and/or fibers, etc. above the T_(g) such that the particles, etc. coalesce to form a shape and cooling the coalesced shape. The temperature and pressure used for coalescing may depend, for example, upon composition of the amorphous material and the desired density of the resulting material. The temperature should below glass crystallization temperature, and for glasses, greater than the glass transition temperature. In certain embodiments, the heating is conducted at at least one temperature in a range of about 850° C. to about 1100° C. (in some embodiments, preferably 900° C. to 1000° C.). Typically, the amorphous material is under pressure (e.g., greater than zero to 1 GPa or more) during coalescence to aid the coalescence of the amorphous material. In one embodiment, a charge of the particles, etc. is placed into a die and hot-pressing is performed at temperatures above glass transition where viscous flow of glass leads to coalescence into a relatively large part. Examples of typical coalescing techniques include hot pressing, hot isostatic pressure, hot extrusion and the like. Typically, it is generally preferred to cool the resulting coalesced body before further heat treatment. After heat treatment if so desired, the coalesced body may be crushed to smaller particle sizes or a desired particle size distribution.

[0098] It is also within the scope of the present invention to conduct additional heat-treatment to further improve desirable properties of the material. For example, hot-isostatic pressing may be conducted (e.g., at temperatures from about 900° C. to about 1400° C.) to remove residual porosity, increasing the density of the material. Optionally, the resulting, coalesced article can be heat-treated to provide glass-ceramic, crystalline ceramic, or ceramic otherwise comprising crystalline ceramic.

[0099] Coalescence of the amorphous material and/or glass-ceramic (e.g., particles) may also be accomplished by a variety of methods, including pressureless or pressure sintering (e.g., sintering, plasma assisted sintering, hot pressing, HIPing, hot forging, hot extrusion, etc.).

[0100] Heat-treatment can be carried out in any of a variety of ways, including those known in the art for heat-treating glass to provide glass-ceramics. For example, heat-treatment can be conducted in batches, for example, using resistive, inductively or gas heated furnaces. Alternatively, for example, heat-treatment can be conducted continuously, for example, using rotary kilns. In the case of a rotary kiln, the material is fed directly into a kiln operating at the elevated temperature. The time at the elevated temperature may range from a few seconds (in some embodiments even less than 5 seconds) to a few minutes to several hours. The temperature may range anywhere from 900° C. to 1600° C., typically between 1200° C. to 1500° C. It is also within the scope of the present invention to perform some of the heat-treatment in batches (e.g., for the nucleation step) and another continuously (e.g., for the crystal growth step and to achieve the desired density). For the nucleation step, the temperature typically ranges between about 900° C. to about 1100° C., in some embodiments, preferably in a range from about 925° C. to about 1050° C. Likewise for the density step, the temperature typically is in a range from about 1100° C. to about 1600° C., in some embodiments, preferably in a range from about 1200° C. to about 1500° C. This heat treatment may occur, for example, by feeding the material directly into a furnace at the elevated temperature. Alternatively, for example, the material may be feed into a furnace at a much lower temperature (e.g., room temperature) and then heated to desired temperature at a predetermined heating rate. It is within the scope of the present invention to conduct heat-treatment in an atmosphere other than air. In some cases it might be even desirable to heat-treat in a reducing atmosphere(s). Also, for, example, it may be desirable to heat-treat under gas pressure as in, for example, hot-isostatic press, or in gas pressure furnace. It is within the scope of the present invention to convert (e.g., crush) the resulting article or heat-treated article to provide particles (e.g., abrasive particles).

[0101] The amorphous material is heat-treated to at least partially crystallize the amorphous material to provide glass-ceramic. The heat-treatment of certain glasses to form glass-ceramics is well known in the art. The heating conditions to nucleate and grow glass-ceramics are known for a variety of glasses. Alternatively, one skilled in the art can determine the appropriate conditions from a Time-Temperature-Transformation (TTT) study of the glass using techniques known in the art. One skilled in the art, after reading the disclosure of the present invention should be able to provide TTT curves for glasses according to the present invention, determine the appropriate nucleation and/or crystal growth conditions to provide glass-ceramics according to the present invention.

[0102] Typically, glass-ceramics are stronger than the amorphous materials from which they are formed. Hence, the strength of the material may be adjusted, for example, by the degree to which the amorphous material is converted to crystalline ceramic phase(s). Alternatively, or in addition, the strength of the material may also be affected, for example, by the number of nucleation sites created, which may in turn be used to affect the number, and in turn the size of the crystals of the crystalline phase(s). For additional details regarding forming glass-ceramics, see, for example Glass-Ceramics, P. W. McMillan, Academic Press, Inc., 2^(nd) edition, 1979, the disclosure of which is incorporated herein by reference.

[0103] For example, during heat-treatment of some exemplary amorphous materials for making glass-ceramics according to present invention, formation of phases such as La₂Zr₂O₇, and, if ZrO₂ is present, cubic/tetragonal ZrO₂, in some cases monoclinic ZrO₂, have been observed at temperatures above about 900° C. Although not wanting to be bound by theory, it is believed that zirconia-related phases are the first phases to nucleate from the amorphous material. Formation of Al₂O₃, ReAlO₃ (wherein Re is at least one rare earth cation), ReAl₁₁O₁₈, Re₃Al₅O₁₂, Y₃Al₅O₁₂, etc. phases are believed to generally occur at temperatures above about 925° C. Typically, crystallite size during this nucleation step is on order of nanometers. For example, crystals as small as 10-15 nanometers have been observed. For at least some embodiments, heat-treatment at about 1300° C. for about 1 hour provides a full crystallization. In generally, heat-treatment times for each of the nucleation and crystal growth steps may range of a few seconds (in some embodiments even less than 5 seconds) to several minutes to an hour or more.

[0104] The size of the resulting crystals can typically controlled at least in part by the nucleation and/or crystallization times and/or temperatures. Although it is generally preferred to have small crystals (e.g., on the order not greater than a micrometer, or even not greater than a nanometer) glass-ceramics according to the present invention may be made with larger crystal sizes (e.g., at least 1-10 micrometers, at least 10-25 micrometers, at least 50-100 micrometers, or even grater than 100 micrometers). Although not wanting to be bound by theory, it is generally believed in the art that the finer the size of the crystals (for the same density), the higher the mechanical properties (e.g., hardness and strength) of the ceramic.

[0105] Examples of crystalline phases which may be present in embodiments of glass-ceramics according to the present invention include: Al₂O₃ (e.g., α-Al₂O₃), Y₂O₃, REO, HfO₂ ZrO₂ (e.g., cubic ZrO₂ and tetragonal ZrO₂), BaO, CaO, Cr₂O₃, CoO, Fe₂O₃, GeO₂, Li₂O, MgO, MnO, NiO, Na₂O, P₂O₅, Sc₂O₃, SiO₂, SrO, TeO₂, TiO₂, V₂O₃, Y₂O₃, ZnO, “complex metal oxides” (including “complex Al₂O₃.metal oxide (e.g., complex Al₂O₃.REO (e.g., ReAlO₃ (e.g., GdAlO₃ LaAlO₃), ReAl₁₁O₁₈ (e.g., LaAl₁₁O₁₈,), and Re₃Al₅O₁₂ (e.g., Dy₃Al₅O₁₂)), complex Al₂O₃.Y₂O₃ (e.g., Y₃Al₅O₁₂), and complex ZrO₂.REO (e.g., Re₂Zr₂O₇ (e.g., La₂Zr₂O₇))), and combinations thereof.

[0106] It is also with in the scope of the present invention to substitute a portion of the yttrium and/or aluminum cations in a complex Al₂O₃.metal oxide (e.g., complex Al₂O₃.Y₂O₃ (e.g., yttrium aluminate exhibiting a garnet crystal structure)) with other cations. For example, a portion of the Al cations in a complex Al₂O₃.Y₂O₃ may be substituted with at least one cation of an element selected from the group consisting of: Cr, Ti, Sc, Fe, Mg, Ca, Si, Co, and combinations thereof. For example, a portion of the Y cations in a complex Al₂O₃.Y₂O₃ may be substituted with at least one cation of an element selected from the group consisting of: Ce, Dy, Er, Eu, Gd, Ho, La, Lu, Nd, Pr, Sm, Th, Tm, Yb, Fe, Ti, Mn, V, Cr, Co, Ni, Cu, Mg, Ca, Sr, and combinations thereof. Similarly, it is also with in the scope of the present invention to substitute a portion of the aluminum cations in alumina. For example, Cr, Ti, Sc, Fe, Mg, Ca, Si, and Co can substitute for aluminum in the alumina. The substitution of cations as described above may affect the properties (e.g. hardness, toughness, strength, thermal conductivity, etc.) of the fused material.

[0107] It is also with in the scope of the present invention to substitute a portion of the rare earth and/or aluminum cations in a complex Al₂O₃.metal oxide (e.g., complex Al₂O₃.REO) with other cations. For example, a portion of the Al cations in a complex Al₂O₃.REO may be substituted with at least one cation of an element selected from the group consisting of: Cr, Ti, Sc, Fe, Mg, Ca, Si, Co, and combinations thereof. For example, a portion of the Y cations in a complex Al₂O₃.REO may be substituted with at least one cation of an element selected from the group consisting of: Y, Fe, Ti, Mn, V, Cr, Co, Ni, Cu, Mg, Ca, Sr, and combinations thereof. Similarly, it is also with in the scope of the present invention to substitute a portion of the aluminum cations in alumina. For example, Cr, Ti, Sc, Fe, Mg, Ca, Si, and Co can substitute for aluminum in the alumina. The substitution of cations as described above may affect the properties (e.g. hardness, toughness, strength, thermal conductivity, etc.) of the fused material.

[0108] The average crystal size can be determined by the line intercept method according to the ASTM standard E 112-96 “Standard Test Methods for Determining Average Grain Size”. The sample is mounted in mounting resin (such as that obtained under the trade designation “TRANSOPTIC POWDER” from Buehler, Lake Bluff, Ill.) typically in a cylinder of resin about 2.5 cm in diameter and about 1.9 cm high. The mounted section is prepared using conventional polishing techniques using a polisher (such as that obtained from Buehler, Lake Bluff, Ill. under the trade designation “ECOMET 3”). The sample is polished for about 3 minutes with a diamond wheel, followed by 5 minutes of polishing with each of 45, 30, 15, 9, 3, and 1-micrometer slurries. The mounted and polished sample is sputtered with a thin layer of gold-palladium and viewed using a scanning electron microscopy (such as the JEOL SEM Model JSM 840A). A typical back-scattered electron (BSE) micrograph of the microstructure found in the sample is used to determine the average crystal size as follows. The number of crystals that intersect per unit length (N_(L)) of a random straight line drawn across the micrograph are counted. The average crystal size is determined from this number using the following equation. ${{Average}\quad {Crystal}\quad {Size}} = \frac{1.5}{N_{L}M}$

[0109] Where N_(L) is the number of crystals intersected per unit length and M is the magnification of the micrograph.

[0110] Some embodiments of the present invention include glass-ceramics comprising alpha alumina having at least one of an average crystal size not greater than 150 nanometers.

[0111] Some embodiments of the present invention include glass-ceramics comprising alpha alumina, wherein at least 90 (in some embodiments preferably, 95, or even 100) percent by number of the alpha alumina present in such portion have crystal sizes not greater than 200 nanometers.

[0112] Some embodiments of the present invention include glass-ceramics comprising alpha Al₂O₃, crystalline ZrO₂, and a first complex Al₂O₃.Y₂O₃, and wherein at least one of the alpha Al₂O₃, the crystalline ZrO₂, or the first complex Al₂O₃.Y₂O₃ has an average crystal size not greater than 150 nanometers. In some embodiments preferably, the glass-ceramics further comprise a second, different complex Al₂O₃.Y₂O₃. In some embodiments preferably, the glass-ceramics further comprise a complex Al₂O₃.REO.

[0113] Some embodiments of the present invention include glass-ceramics comprising a first complex Al₂O₃.Y₂O₃, a second, different complex Al₂O₃.Y₂O₃, and crystalline ZrO₂, and wherein for at least one of the first complex Al₂O₃.Y₂O₃, the second complex Al₂O₃.Y₂O₃, or the crystalline ZrO₂, at least 90 (in some embodiments preferably, 95, or even 100) percent by number of the crystal sizes thereof are not greater than 200 nanometers. In some embodiments preferably, the glass-ceramics further comprise a second, different complex Al₂O₃.Y₂O₃. In some embodiments preferably, the glass-ceramics further comprise a complex Al₂O₃.REO.

[0114] Some embodiments of the present invention include glass-ceramics comprising alpha Al₂O₃, crystalline ZrO₂, and a first complex Al₂O₃.REO, and wherein at least one of the alpha Al₂O₃, the crystalline ZrO₂, or the first complex Al₂O₃.REO has an average crystal size not greater than 150 nanometers. In some embodiments preferably, the glass-ceramics further comprise a second, different complex Al₂O₃.REO. In some embodiments preferably, the glass-ceramics further comprise a complex Al₂O₃.Y₂O₃.

[0115] Some embodiments of the present invention include glass-ceramics comprising a first complex Al₂O₃.REO, a second, different complex Al₂O₃.REO, and crystalline ZrO₂, and wherein for at least one of the first complex Al₂O₃.REO, the second complex Al₂O₃.REO, or the crystalline ZrO₂, at least 90 (in some embodiments preferably, 95, or even 100) percent by number of the crystal sizes thereof are not greater than 200 nanometers. In some embodiments preferably, the glass-ceramics further comprise a complex Al₂O₃.Y₂O₃.

[0116] Some embodiments of the present invention include glass-ceramics comprising a first complex Al₂O₃.Y₂O₃, a second, different complex Al₂O₃.Y₂O₃, and crystalline ZrO₂, and wherein at least one of the first complex Al₂O₃.Y₂O₃, the second, different complex Al₂O₃-Y₂O₃, or the crystalline ZrO₂ has an average crystal size not greater than 150 nanometers. In some embodiments preferably, the glass-ceramics further comprise a second, different complex Al₂O₃.Y₂O₃. In some embodiments preferably, the glass-ceramics further comprise a complex Al₂O₃.REO.

[0117] Some embodiments of the present invention include glass-ceramics comprising a first complex Al₂O₃.Y₂O₃, a second, different complex Al₂O₃.Y₂O₃, and crystalline ZrO₂, and wherein for at least one of the first complex Al₂O₃.Y₂O₃, the second, different complex Al₂O₃.Y₂O₃, or the crystalline ZrO₂, at least 90 (in some embodiments preferably, 95, or even 100) percent by number of the crystal sizes thereof are not greater than 200 nanometers. In some embodiments preferably, the glass-ceramics further comprise a complex Al₂O₃.REO.

[0118] Some embodiments of the present invention include glass-ceramics comprising a first complex Al₂O₃.REO, a second, different complex Al₂O₃.REO, and crystalline ZrO₂, and wherein at least one of the first complex Al₂O₃.REO, the second, different complex Al₂O₃.REO, or the crystalline ZrO₂ has an average crystal size not greater than 150 nanometers. In some embodiments preferably, the glass-ceramics further comprise a second, different complex Al₂O₃.REO. In some embodiments preferably, the glass-ceramics further comprise a complex Al₂O₃.Y₂O₃.

[0119] Some embodiments of the present invention include glass-ceramics comprising a first complex Al₂O₃.REO, a second, different complex Al₂O₃.REO, and crystalline ZrO₂, and wherein for at least one of the first complex Al₂O₃.REO, the second, different complex Al₂O₃.REO, or the crystalline ZrO₂, at least 90 (in some embodiments preferably, 95, or even 100) percent by number of the crystal sizes thereof are not greater than 200 nanometers. In some embodiments preferably, the glass-ceramics further comprise a complex Al₂O₃.Y₂O₃.

[0120] In some embodiments, glass-ceramics according to the present invention comprise at least 75, 80, 85, 90, 95, 97, 98, 99, or even 100 percent by volume crystallites, wherein the crystallites have an average size of less than 1 micrometer. In some embodiments, glass-ceramics according to the present invention comprise not greater than at least 75, 80, 85, 90, 95, 97, 98, 99, or even 100 percent by volume crystallites, wherein the crystallites have an average size not greater than 0.5 micrometer. In some embodiments, glass-ceramics according to the present invention comprise less than at 75, 80, 85, 90, 95, 97, 98, 99, or even 100 percent by volume crystallites, wherein the crystallites have an average size not greater than 0.3 micrometer. In some embodiments, glass-ceramics according to the present invention comprise less than at least 75, 80, 85, 90, 95, 97, 98, 99, or even 100 percent by volume crystallites, wherein the crystallites have an average size not greater than 0.15 micrometer.

[0121] Crystals formed by heat-treating amorphous to provide embodiments of glass-ceramics according to the present invention may be, for example, equiaxed, columnar, or flattened splat-like features.

[0122] Although an amorphous material, glass-ceramic, etc. according to the present invention may be in the form of a bulk material, it is also within the scope of the present invention to provide composites comprising an amorphous material, glass-ceramic, etc. according to the present invention. Such a composite may comprise, for example, a phase or fibers (continuous or discontinuous) or particles (including whiskers) (e.g., metal oxide particles, boride particles, carbide particles, nitride particles, diamond particles, metallic particles, glass particles, and combinations thereof) dispersed in an amorphous material, glass-ceramic, etc. according to the present invention, invention or a layered-composite structure (e.g., a gradient of glass-ceramic to amorphous material used to make the glass-ceramic and/or layers of different compositions of glass-ceramics).

[0123] Typically, the (true) density, sometimes referred to as specific gravity, of ceramics according to the present invention is typically at least 70% of theoretical density. More desirably, the (true) density of ceramic according to the present invention is at least 75%, 80%, 85%, 90%, 92%, 95%, 96%, 97%, 98%, 99%, 99.5% or even 100% of theoretical density. Abrasive particles according to the present invention have densities of at least 85%, 90%, 92%, 95%, 96%, 97%, 98%, 99%, 99.5% or even 100% of theoretical density.

[0124] The average hardness of the material of the present invention can be determined as follows. Sections of the material are mounted in mounting resin (obtained under the trade designation “TRANSOPTIC POWDER” from Buehler, Lake Bluff, Ill.) typically in a cylinder of resin about 2.5 cm in diameter and about 1.9 cm high. The mounted section is prepared using conventional polishing techniques using a polisher (such as that obtained from Buehler, Lake Bluff, Ill. under the trade designation “ECOMET 3”). The sample is polished for about 3 minutes with a diamond wheel, followed by 5 minutes of polishing with each of 45, 30, 15, 9, 3, and 1-micrometer slurries. The microhardness measurements are made using a conventional microhardness tester (such as that obtained under the trade designation “MITUTOYO MVK-VL” from Mitutoyo Corporation, Tokyo, Japan) fitted with a Vickers indenter using a 100-gram indent load. The microhardness measurements are made according to the guidelines stated in ASTM Test Method E384 Test Methods for Microhardness of Materials (1991), the disclosure of which is incorporated herein by reference.

[0125] In some embodiments, glass-ceramic according to the present invention have an average hardness of at least 13 GPa (in some embodiments preferably, at least 14, 15, 16, 17, or even at least 18 GPa). Abrasive particles according to the present invention have an average hardness of at least 15 GPa, in some embodiments, at least 16 GPa, at least 17 GPa, or even at least 18 GPa.

[0126] Additional details regarding amorphous materials and glass-ceramics, including making, using, and properties thereof, can be found in application having U.S. Ser. Nos. 09/922,526, 09/922,527, and 09/922,530, filed Aug. 2, 2001, and U.S. Ser. No. ______(Attorney Docket Nos. 56931US005, 56931US006, 56931US007, 56931US008, 56931US009, 57980US002, and 57981US002, filed the same date as the instant application, the disclosures of which are incorporated herein by reference.

[0127] Abrasive particles according to the present invention generally comprise crystalline ceramic (in some embodiments, preferably at least 75, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.5, or even 100 percent by volume) crystalline ceramic.

[0128] Abrasive particles according to the present invention can be screened and graded using techniques well known in the art, including the use of industry recognized grading standards such as ANSI (American National Standard Institute), FEPA (Federation Europeenne des Fabricants de Products Abrasifs), and JIS (Japanese Industrial Standard). Abrasive particles according to the present invention may be used in a wide range of particle sizes, typically ranging in size from about 0.1 to about 5000 micrometers, more typically from about 1 to about 2000 micrometers; desirably from about 5 to about 1500 micrometers, more desirably from about 100 to about 1500 micrometers.

[0129] ANSI grade designations include: ANSI 4, ANSI 6, ANSI 8, ANSI 16, ANSI 24, ANSI 36, ANSI 40, ANSI 50, ANSI 60, ANSI 80, ANSI 100, ANSI 120, ANSI 150, ANSI 180, ANSI 220, ANSI 240, ANSI 280, ANSI 320, ANSI 360, ANSI 400, and ANSI 600. Preferred ANSI grades comprising abrasive particles according to the present invention are ANSI 8-220. FEPA grade designations include P8, P12, P16, P24, P36, P40, P50, P60, P80, P100, P120, P150, P180, P220, P320, P400, P500, P600, P800, P1000, and P1200. Preferred FEPA grades comprising abrasive particles according to the present invention are P12-P220. JIS grade designations include JIS8, JIS12, JIS16, JIS24, JIS36, JIS46, JIS54, JIS60, JIS80, JIS10, JIS150, JIS180, JIS220, JIS240, JIS280, JIS320, JIS360, JIS400, JIS400, JIS600, JIS800, JIS1000, JIS1500, JIS2500, JIS4000, JIS6000, JIS8000, and JIS10,000. Preferred JIS grades comprising abrasive particles according to the present invention are JIS8-220.

[0130] After crushing and screening, there will typically be a multitude of different abrasive particle size distributions or grades. These multitudes of grades may not match a manufacturer's or supplier's needs at that particular time. To minimize inventory, it is possible to recycle the off demand grades back into melt to form amorphous material. This recycling may occur after the crushing step, where the particles are in large chunks or smaller pieces (sometimes referred to as “fines”) that have not been screened to a particular distribution.

[0131] In another aspect, the present invention provides a method for making abrasive particles, the method comprising heat-treating amorphous (e.g., glass) comprising particles such that at least a portion of the amorphous material converts to a glass-ceramic to provide abrasive particles comprising the glass-ceramic. The present invention also provides a method for making abrasive particles comprising a glass-ceramic, the method comprising heat-treating amorphous material such that at least a portion of the amorphous material converts to a glass-ceramic, and crushing the resulting heat-treated material to provide the abrasive particles. When crushed, glass tends to provide sharper particles than crushing significantly crystallized glass-ceramics or crystalline material.

[0132] In another aspect, the present invention provides agglomerate abrasive grains each comprise a plurality of abrasive particles according to the present invention bonded together via a binder. In another aspect, the present invention provides an abrasive article (e.g., coated abrasive articles, bonded abrasive articles (including vitrified, resinoid, and metal bonded grinding wheels, cutoff wheels, mounted points, and honing stones), nonwoven abrasive articles, and abrasive brushes) comprising a binder and a plurality of abrasive particles, wherein at least a portion of the abrasive particles are abrasive particles (including where the abrasive particles are agglomerated) according to the present invention. Methods of making such abrasive articles and using abrasive articles are well known to those skilled in the art. Furthermore, abrasive particles according to the present invention can be used in abrasive applications that utilize abrasive particles, such as slurries of abrading compounds (e.g., polishing compounds), milling media, shot blast media, vibratory mill media, and the like.

[0133] Coated abrasive articles generally include a backing, abrasive particles, and at least one binder to hold the abrasive particles onto the backing. The backing can be any suitable material, including cloth, polymeric film, fibre, nonwoven webs, paper, combinations thereof, and treated versions thereof. The binder can be any suitable binder, including an inorganic or organic binder (including thermally curable resins and radiation curable resins). The abrasive particles can be present in one layer or in two layers of the coated abrasive article.

[0134] An example of a coated abrasive article according to the present invention is depicted in FIG. 1. Referring to this figure, coated abrasive article according to the present invention 1 has a backing (substrate) 2 and abrasive layer 3. Abrasive layer 3 includes abrasive particles according to the present invention 4 secured to a major surface of backing 2 by make coat 5 and size coat 6. In some instances, a supersize coat (not shown) is used.

[0135] Bonded abrasive articles typically include a shaped mass of abrasive particles held together by an organic, metallic, or vitrified binder. Such shaped mass can be, for example, in the form of a wheel, such as a grinding wheel or cutoff wheel. The diameter of grinding wheels typically is about 1 cm to over 1 meter; the diameter of cut off wheels about 1 cm to over 80 cm (more typically 3 cm to about 50 cm). The cut off wheel thickness is typically about 0.5 mm to about 5 cm, more typically about 0.5 mm to about 2 cm. The shaped mass can also be in the form, for example, of a honing stone, segment, mounted point, disc (e.g. double disc grinder) or other conventional bonded abrasive shape. Bonded abrasive articles typically comprise about 3-50% by volume bond material, about 30-90% by volume abrasive particles (or abrasive particle blends), up to 50% by volume additives (including grinding aids), and up to 70% by volume pores, based on the total volume of the bonded abrasive article.

[0136] A preferred form is a grinding wheel. Referring to FIG. 2, grinding wheel according to the present invention 10 is depicted, which includes abrasive particles according to the present invention 11, molded in a wheel and mounted on hub 12.

[0137] Nonwoven abrasive articles typically include an open porous lofty polymer filament structure having abrasive particles according to the present invention distributed throughout the structure and adherently bonded therein by an organic binder. Examples of filaments include polyester fibers, polyamide fibers, and polyaramid fibers. In FIG. 3, a schematic depiction, enlarged about 100×, of a typical nonwoven abrasive article according to the present invention is provided. Such a nonwoven abrasive article according to the present invention comprises fibrous mat 50 as a substrate, onto which abrasive particles according to the present invention 52 are adhered by binder 54.

[0138] Useful abrasive brushes include those having a plurality of bristles unitary with a backing (see, e.g., U.S. Pat. Nos. 5,427,595 (Pihl et al.), 5,443,906 (Pihl et al.), 5,679,067 (Johnson et al.), and 5,903,951 (Ionta et al.), the disclosure of which is incorporated herein by reference). Desirably, such brushes are made by injection molding a mixture of polymer and abrasive particles.

[0139] Suitable organic binders for making abrasive articles include thermosetting organic polymers. Examples of suitable thermosetting organic polymers include phenolic resins, urea-formaldehyde resins, melamine-formaldehyde resins, urethane resins, acrylate resins, polyester resins, aminoplast resins having pendant α,β-unsaturated carbonyl groups, epoxy resins, acrylated urethane, acrylated epoxies, and combinations thereof. The binder and/or abrasive article may also include additives such as fibers, lubricants, wetting agents, thixotropic materials, surfactants, pigments, dyes, antistatic agents (e.g., carbon black, vanadium oxide, graphite, etc.), coupling agents (e.g., silanes, titanates, zircoaluminates, etc.), plasticizers, suspending agents, and the like. The amounts of these optional additives are selected to provide the desired properties. The coupling agents can improve adhesion to the abrasive particles and/or filler. The binder chemistry may thermally cured, radiation cured or combinations thereof. Additional details on binder chemistry may be found in U.S. Pat. Nos. 4,588,419 (Caul et al.), 4,751,138 (Tumey et al.), and 5,436,063 (Follett et al.), the disclosures of which are incorporated herein by reference.

[0140] More specifically with regard to vitrified bonded abrasives, vitreous bonding materials, which exhibit an amorphous structure and are typically hard, are well known in the art. In some cases, the vitreous bonding material includes crystalline phases. Bonded, vitrified abrasive articles according to the present invention may be in the shape of a wheel (including cut off wheels), honing stone, mounted pointed or other conventional bonded abrasive shape. A preferred vitrified bonded abrasive article according to the present invention is a grinding wheel.

[0141] Examples of metal oxides that are used to form vitreous bonding materials include: silica, silicates, alumina, soda, calcia, potassia, titania, iron oxide, zinc oxide, lithium oxide, magnesia, boria, aluminum silicate, borosilicate glass, lithium aluminum silicate, combinations thereof, and the like. Typically, vitreous bonding materials can be formed from composition comprising from 10 to 100% glass frit, although more typically the composition comprises 20% to 80% glass frit, or 30% to 70% glass frit. The remaining portion of the vitreous bonding material can be a non-frit material. Alternatively, the vitreous bond may be derived from a non-frit containing composition. Vitreous bonding materials are typically matured at a temperature(s) in a range of about 700° C. to about 1500° C., usually in a range of about 800° C. to about 1300° C., sometimes in a range of about 900° C. to about 1200° C., or even in a range of about 950° C. to about 1100C. The actual temperature at which the bond is matured depends, for example, on the particular bond chemistry.

[0142] Preferred vitrified bonding materials may include those comprising silica, alumina (desirably, at least 10 percent by weight alumina), and boria (desirably, at least 10 percent by weight boria). In most cases the vitrified bonding material further comprise alkali metal oxide(s) (e.g., Na₂O and K₂O) (in some cases at least 10 percent by weight alkali metal oxide(s)).

[0143] Binder materials may also contain filler materials or grinding aids, typically in the form of a particulate material. Typically, the particulate materials are inorganic materials. Examples of useful fillers for this invention include: metal carbonates (e.g., calcium carbonate (e.g., chalk, calcite, marl, travertine, marble and limestone), calcium magnesium carbonate, sodium carbonate, magnesium carbonate), silica (e.g., quartz, glass beads, glass bubbles and glass fibers) silicates (e.g., talc, clays, (montmorillonite) feldspar, mica, calcium silicate, calcium metasilicate, sodium aluminosilicate, sodium silicate) metal sulfates (e.g., calcium sulfate, barium sulfate, sodium sulfate, aluminum sodium sulfate, aluminum sulfate), gypsum, vermiculite, wood flour, aluminum trihydrate, carbon black, metal oxides (e.g., calcium oxide (lime), aluminum oxide, titanium dioxide), and metal sulfites (e.g., calcium sulfite).

[0144] In general, the addition of a grinding aid increases the useful life of the abrasive article. A grinding aid is a material that has a significant effect on the chemical and physical processes of abrading, which results in improved performance. Although not wanting to be bound by theory, it is believed that a grinding aid(s) will (a) decrease the friction between the abrasive particles and the workpiece being abraded, (b) prevent the abrasive particles from “capping” (i.e., prevent metal particles from becoming welded to the tops of the abrasive particles), or at least reduce the tendency of abrasive particles to cap, (c) decrease the interface temperature between the abrasive particles and the workpiece, or (d) decreases the grinding forces.

[0145] Grinding aids encompass a wide variety of different materials and can be inorganic or organic based. Examples of chemical groups of grinding aids include waxes, organic halide compounds, halide salts and metals and their alloys. The organic halide compounds will typically break down during abrading and release a halogen acid or a gaseous halide compound. Examples of such materials include chlorinated waxes like tetrachloronaphtalene, pentachloronaphthalene, and polyvinyl chloride. Examples of halide salts include sodium chloride, potassium cryolite, sodium cryolite, ammonium cryolite, potassium tetrafluoroboate, sodium tetrafluoroborate, silicon fluorides, potassium chloride, and magnesium chloride. Examples of metals include, tin, lead, bismuth, cobalt, antimony, cadmium, and iron titanium. Other miscellaneous grinding aids include sulfur, organic sulfur compounds, graphite, and metallic sulfides. It is also within the scope of the present invention to use a combination of different grinding aids, and in some instances this may produce a synergistic effect. The preferred grinding aid is cryolite; the most preferred grinding aid is potassium tetrafluoroborate.

[0146] Grinding aids can be particularly useful in coated abrasive and bonded abrasive articles. In coated abrasive articles, grinding aid is typically used in the supersize coat, which is applied over the surface of the abrasive particles. Sometimes, however, the grinding aid is added to the size coat. Typically, the amount of grinding aid incorporated into coated abrasive articles are about 50-300 g/m² (desirably, about 80-160 g/m²). In vitrified bonded abrasive articles grinding aid is typically impregnated into the pores of the article.

[0147] The abrasive articles can contain 100% abrasive particles according to the present invention, or blends of such abrasive particles with other abrasive particles and/or diluent particles. However, at least about 2% by weight, desirably at least about 5% by weight, and more desirably about 30-100% by weight, of the abrasive particles in the abrasive articles should be abrasive particles according to the present invention. In some instances, the abrasive particles according the present invention may be blended with another abrasive particles and/or diluent particles at a ratio between 5 to 75% by weight, about 25 to 75% by weight about 40 to 60% by weight, or about 50% to 50% by weight (i.e., in equal amounts by weight). Examples of suitable conventional abrasive particles include fused aluminum oxide (including white fused alumina, heat-treated aluminum oxide and brown aluminum oxide), silicon carbide, boron carbide, titanium carbide, diamond, cubic boron nitride, garnet, fused alumina-zirconia, and sol-gel-derived abrasive particles, and the like. The sol-gel-derived abrasive particles may be seeded or non-seeded. Likewise, the sol-gel-derived abrasive particles may be randomly shaped or have a shape associated with them, such as a rod or a triangle. Examples of sol gel abrasive particles include those described U.S. Pat. Nos. 4,314,827 (Leitheiser et al.), 4,518,397 (Leitheiser et al.), 4,623,364 (Cottringer et al.), 4,744,802 (Schwabel), 4,770,671 (Monroe et al.), 4,881,951 (Wood et al.), 5,011,508 (Wald et al.), 5,090,968 (Pellow), 5,139,978 (Wood), 5,201,916 (Berg et al.), 5,227,104 (Bauer), 5,366,523 (Rowenhorst et al.), 5,429,647 (Larmie), 5,498,269 (Larmie), and 5,551,963 (Larmie), the disclosures of which are incorporated herein by reference. Additional details concerning sintered alumina abrasive particles made by using alumina powders as a raw material source can also be found, for example, in U.S. Pat. Nos. 5,259,147 (Falz), 5,593,467 (Monroe), and 5,665,127 (Moltgen), the disclosures of which are incorporated herein by reference. Additional details concerning fused abrasive particles, can be found, for example, in U.S. Pat. Nos. 1,161,620 (Coulter), 1,192,709 (Tone), 1,247,337 (Saunders et al.), 1,268,533 (Allen), and 2,424,645 (Baumann et al.) 3,891,408 (Rowse et al.), 3,781,172 (Pett et al.), 3,893,826 (Quinan et al.), 4,126,429 (Watson), 4,457,767 (Poon et al.), 5,023,212 (Dubots et. al), 5,143,522 (Gibson et al.), and 5,336,280 (Dubots et. al), and applications having U.S. Serial Nos. 09,495,978, 09/496,422, 09/496,638, and 09/496,713, each filed on Feb. 2, 2000, and, 09/618,876, 09/618,879, 09/619,106, 09/619,191, 09/619,192, 09/619,215, 09/619,289, 09/619,563, 09/619,729, 09/619,744, and 09/620,262, each filed on Jul. 19, 2000, and Ser. No. 09/772,730, filed Jan. 30, 2001, the disclosures of which are incorporated herein by reference. In some instances, blends of abrasive particles may result in an abrasive article that exhibits improved grinding performance in comparison with abrasive articles comprising 100% of either type of abrasive particle.

[0148] If there is a blend of abrasive particles, the abrasive particle types forming the blend may be of the same size. Alternatively, the abrasive particle types may be of different particle sizes. For example, the larger sized abrasive particles may be abrasive particles according to the present invention, with the smaller sized particles being another abrasive particle type. Conversely, for example, the smaller sized abrasive particles may be abrasive particles according to the present invention, with the larger sized particles being another abrasive particle type.

[0149] Examples of suitable diluent particles include marble, gypsum, flint, silica, iron oxide, aluminum silicate, glass (including glass bubbles and glass beads), alumina bubbles, alumina beads and diluent agglomerates. Abrasive particles according to the present invention can also be combined in or with abrasive agglomerates. Abrasive agglomerate particles typically comprise a plurality of abrasive particles, a binder, and optional additives. The binder may be organic and/or inorganic. Abrasive agglomerates may be randomly shape or have a predetermined shape associated with them. The shape may be a block, cylinder, pyramid, coin, square, or the like. Abrasive agglomerate particles typically have particle sizes ranging from about 100 to about 5000 micrometers, typically about 250 to about 2500 micrometers. Additional details regarding abrasive agglomerate particles may be found, for example, in U.S. Pat. Nos. 4,311,489 (Kressner), 4,652,275 (Bloecher et al.), 4,799,939 (Bloecher et al.), 5,549,962 (Holmes et al.), and 5,975,988 (Christianson), and applications having U.S. Ser. Nos. 09/688,444 and 09/688,484, filed Oct. 16, 2000, the disclosures of which are incorporated herein by reference.

[0150] The abrasive particles may be uniformly distributed in the abrasive article or concentrated in selected areas or portions of the abrasive article. For example, in a coated abrasive, there may be two layers of abrasive particles. The first layer comprises abrasive particles other than abrasive particles according to the present invention, and the second (outermost) layer comprises abrasive particles according to the present invention. Likewise in a bonded abrasive, there may be two distinct sections of the grinding wheel. The outermost section may comprise abrasive particles according to the present invention, whereas the innermost section does not. Alternatively, abrasive particles according to the present invention may be uniformly distributed throughout the bonded abrasive article.

[0151] Further details regarding coated abrasive articles can be found, for example, in U.S. Pat. Nos. 4,734,104 (Broberg), 4,737,163 (Larkey), 5,203,884 (Buchanan et al.), 5,152,917 (Pieper et al.), 5,378,251 (Culler et al.), 5,417,726 (Stout et al.), 5,436,063 (Follett et al.), 5,496,386 (Broberg et al.), 5, 609,706 (Benedict et al.), 5,520,711 (Helmin), 5,954,844 (Law et al.), 5,961,674 (Gagliardi et al.), and 5,975,988 (Christinason), the disclosures of which are incorporated herein by reference. Further details regarding bonded abrasive articles can be found, for example, in U.S. Pat. Nos. 4,543,107 (Rue), 4,741,743 (Narayanan et al.), 4,800,685 (Haynes et al.), 4,898,597 (Hay et al.), 4,997,461 (Markhoff-Matheny et al.), 5,037,453 (Narayanan et al.), 5,110,332 (Narayanan et al.), and 5,863,308 (Qi et al.) the disclosures of which are incorporated herein by reference. Further details regarding vitreous bonded abrasives can be found, for example, in U.S. Pat. Nos. 4,543,107 (Rue), 4,898,597 (Hay et al.), 4,997,461 (Markhoff-Matheny et al.), 5,094,672 (Giles Jr. et al.), 5,118,326 (Sheldon et al.), 5,131,926(Sheldon et al.), 5,203,886 (Sheldon et al.), 5,282,875 (Wood et al.), 5,738,696 (Wu et al.), and 5,863,308 (Qi), the disclosures of which are incorporated herein by reference. Further details regarding nonwoven abrasive articles can be found, for example, in U.S. Pat. No. 2,958,593 (Hoover et al.), the disclosure of which is incorporated herein by reference.

[0152] The present invention provides a method of abrading a surface, the method comprising contacting at least one abrasive particle according to the present invention, with a surface of a workpiece; and moving at least of one the abrasive particle or the contacted surface to the other to abrade at least a portion of said surface with the abrasive particle. Methods for abrading with abrasive particles according to the present invention range of snagging (i.e., high pressure high stock removal) to polishing (e.g., polishing medical implants with coated abrasive belts), wherein the latter is typically done with finer grades (e.g., less ANSI 220 and finer) of abrasive particles. The abrasive particle may also be used in precision abrading applications, such as grinding cam shafts with vitrified bonded wheels. The size of the abrasive particles used for a particular abrading application will be apparent to those skilled in the art.

[0153] Abrading with abrasive particles according to the present invention may be done dry or wet. For wet abrading, the liquid may be introduced supplied in the form of a light mist to complete flood. Examples of commonly used liquids include: water, water-soluble oil, organic lubricant, and emulsions. The liquid may serve to reduce the heat associated with abrading and/or act as a lubricant. The liquid may contain minor amounts of additives such as bactericide, antifoaming agents, and the like.

[0154] Abrasive particles according to the present invention may be used to abrade workpieces such as aluminum metal, carbon steels, mild steels, tool steels, stainless steel, hardened steel, titanium, glass, ceramics, wood, wood like materials, paint, painted surfaces, organic coated surfaces and the like. The applied force during abrading typically ranges from about 1 to about 100 kilograms.

[0155] Other examples of uses of embodiments of amorphous materials and/or glass-ceramics according to the present invention include as solid electrolytes in such applications as solid state batteries, solid oxide fuel cells and other electrochemical devices; as hosts for radioactive wastes and surplus actinides; as oxidation catalysts; as oxygen monitoring sensors; as hosts for fluorescence centers; durable IR transmitting window materials; and armor. For example, pyrochlore type of rare earth zirconium oxides (Re₂Zr₂O₇) are known to be useful phases for the above-mentioned radioactive wastes, surplus actinides, oxidation catalysts, oxygen monitoring sensors, and fluorescence centers applications. Further, for example, Ce-containing mixed oxides are known as oxidation catalysts. Although not wanting to be bound by theory, it is believed that the redox properties and the relatively high oxygen storage capacity of the Ce-containing mixed oxides aid in oxidation catalysts. With regard to durable IR transmitting window materials applications uses include those involving moisture, impact by solid and liquid particles, high temperatures, and rapid heating rates.

[0156] Advantages and embodiments of this invention are further illustrated by the following examples, but the particular materials and amounts thereof recited in these examples, as well as other conditions and details, should not be construed to unduly limit this invention. All parts and percentages are by weight unless otherwise indicated. Unless otherwise stated, all examples contained no significant amount of SiO₂, B₂O₃, P₂O₅, GeO₂, TeO₂, As₂O₃, and V₂O₅.

EXAMPLES Example 1

[0157] A 250-ml polyethylene bottle (7.3-cm diameter) was charged with the following 50-gram mixture: 19.3 grams of alumina particles (obtained from Alcoa Industrial Chemicals, Bauxite, Ark., under the trade designation “A16SG”), 9.5 grams of zirconium oxide particles (obtained from Zirconia Sales, Inc. of Marietta, Ga. under the trade designation “DK-2”), and 21.2 grams of lanthanum oxide particles (obtained from Molycorp Inc., Mountain Pass, Calif.), 75 grams of isopropyl alcohol, and 200 grams of alumina milling media (cylindrical in shape, both height and diameter of 0.635 cm; 99.9% alumina; obtained from Coors, Golden, Colo.). The contents of the polyethylene bottle were milled for 16 hours at 60 revolutions per minute (rpm). The ratio of alumina to zirconia in the starting material was 2:1, and the alumina and zirconia collectively made up about 58 weight percent (wt-%). After the milling, the milling media were removed and the slurry was poured onto a warm (approximately 75° C.) glass (“PYREX”) pan and dried. The dried mixture was screened through a 70-mesh screen (212-micrometer opening size) with the aid of a paint brush.

[0158] After grinding and screening, the mixture of milled feed particles was fed slowly (0.5 gram/minute) into a hydrogen/oxygen torch flame to melt the particles. The torch used to melt the particles, thereby generating molten droplets, was a Bethlehem bench burner PM2D Model B obtained from Bethlehem Apparatus Co., Hellertown, Pa. Hydrogen and oxygen flow rates for the torch were as follows. For the inner ring, the hydrogen flow rate was 8 standard liters per minute (SLPM) and the oxygen flow rate was 3.5 SLPM. For the outer ring, the hydrogen flow rate was 23 SLPM and the oxygen flow rate was 12 SLPM. The dried and sized particles were fed slowly (0.5 gram/minute) into the torch flame, which melted the particles and carried them on to an inclined stainless steel surface (approximately 51 centimeters (20 inches) wide with a slope angle of 45 degrees) with cold water running over (approximately 8 liters/minute) the surface to rapidly quench the molten droplets. The resulting molten and quenched beads were collected and dried at 110° C. The particles were spherical in shape and varied in size from a few micrometers (i.e., microns) up to 250 micrometers.

[0159] Subsequently, the flame-formed beads having diameters less than 125 micrometers were then passed through a plasma gun and deposited on stainless steel substrates as follows.

[0160] Four 304 stainless steel substrates (76.2 millimeter (mm)×25.4 mm×3.175 mm dimensions), and two 1080 carbon steel substrates (76.2 mm×25.4 mm×1.15 mm) were prepared in the following manner. The sides to be coated were sandblasted, washed in an ultrasonic bath, and then wiped clean with isopropyl alcohol. Four stainless steel and one 1080 carbon steel substrates were placed approximately 10 centimeters (cm) in front of the nozzle of a plasma gun (obtained under the trade designation “Praxair SG-100 Plasma Gun” from Praxair Surface Technologies, Concord, N.H.). The second 1080 carbon steel was placed 18 cm in front of the nozzle of the plasma gun. The coatings made on the second 1080 carbon steel samples at a distance of 18 cm in front of the nozzle of the plasma gun were not further characterized.

[0161] The plasma unit had a power rating of 40 kW. The plasma gas was argon (50 pounds per square inch (psi), 0.3 megapascal (MPa)) with helium as the auxiliary gas (150 psi, 1 MPa). The beads were passed through the plasma gun by using argon as the carrier gas (50 psi, 0.3 MPa) using a Praxair Model 1270 computerized powder feeder (obtained from Praxair Surface Technologies, Concord, NH). During deposition, a potential of about 40 volts and a current of about 900 amperes was applied and the plasma gun was panned left to right, up and down, to evenly coat the substrates. When the desired thickness was achieved, the plasma spray was shut off and the samples were recovered. The 1080 carbon steel substrate was flexed, thus separating the coating from the substrate resulting in a free-standing bulk material. The deposited material had a z dimension (thickness) of about 1350 micrometers, as determined using optical microscopy.

[0162] The phase composition (glassy/amorphous/crystalline) was determined through Differential Thermal Analysis (DTA) as described below. The material was classified as amorphous if the corresponding DTA trace of the material contained an exothermic crystallization event (T_(x)). If the same trace also contained an endothermic event (T_(g)) at a temperature lower than T_(x) it was considered to consist of a glass phase. If the DTA trace of the material contained no such events, it was considered to contain crystalline phases.

[0163] Differential thermal analysis (DTA) was conducted using the following method. DTA runs were made (using an instrument obtained from Netzsch Instruments, Selb, Germany under the trade designation “NETZSCH STA 409 DTA/TGA”) using a −140+170 mesh size fraction (i.e., the fraction collected between 105-micrometer opening size and 90-micrometer opening size screens). The amount of each screened sample placed in a 100-microliter Al₂O₃ sample holder was about 400 milligrams. Each sample was heated in static air at a rate of 10° C./minute from room temperature (about 25° C.) to 1100° C.

[0164] The coated material (on 304 stainless steel substrates) exhibited an endothermic event at a temperature around 880° C., as evidenced by a downward change in the curve of the trace. It is believed this event was due to the glass transition (T_(g)) of the glass material. The same material exhibited an exothermic event at a temperature around 931° C., as evidenced by a sharp peak in the trace. It is believed that this event was due to the crystallization (T_(x)) of the material. Thus, the coated material (on 304 stainless steel substrates) and the free-standing bulk material were glassy as determined by a DTA trace.

[0165] A portion of the glassy free-standing bulk material was then heat-treated at 1300° C. for 48 hours. Powder X-ray diffraction, XRD, (using an X-ray diffractometer (obtained under the trade designation “PHILLIPS XRG 3100” from Phillips, Mahwah, N.J.) with copper K α1 radiation of 1.54050 Angstrom)) was used to determine the phases present. The phases were determined by comparing the peaks present in the XRD trace of the crystallized material to XRD patterns of crystalline phases provided in JCPDS databases, published by International Center for Diffraction Data. The resulting crystalline material included LaAlO₃, ZrO₂ (cubic, tetragonal), LaAl₁₁O₁₈, and transitional Al₂O₃ phases.

[0166] Another portion of the glassy free-standing bulk material was crystallized at 1300° C. for 1 hour in an electrically heated furnace (obtained from CM Furnaces, Bloomfield, N.J. under the trade designation “Rapid Temp Furnace”). The crystallized coating was crushed with a hammer into particles of −30+35 mesh size (i.e., the fraction collected between 600-micrometer opening size and 500-micrometer opening size screens). The particles were cleaned of debris by washing in a sonic bath (obtained from Cole-Parmer, Vernon Hills, Ill., under the trade designation “8891”) for 15 minutes, dried at 100° C., and several were mounted on a metal cylinder (3 cm in diameter and 2 cm high) using carbon tape. The mounted sample was sputter coated with a thin layer of gold-palladium and viewed using a JEOL scanning electron microscopy (SEM) (Model JSM 840A). The fractured surface was rough and no crystals coarser than 200 nanometers (nm) were observed (see FIG. 4) in the SEM.

Example 2

[0167] Feed particles were made as described in Example 1 using the following 50-gram mixture: 21.5 grams of alumina particles (obtained from Alcoa Industrial Chemicals, Bauxite, Ark. under the trade designation “A16SG”), 9 grams of zirconium oxide particles (obtained from Zirconia Sales, Inc. of Marietta, Ga. under the trade designation “DK-2”), and 19.5 grams of cerium oxide particles (obtained from Rhone-Poulence, France). The ratio of alumina to zirconia in the starting material was 2.4:1 and the alumina and zirconia collectively made up about 61 weight percent. Feed particles were flame-formed into beads (of a size that varied from a few micrometers up to 250 micrometers) as described in Example 1. Subsequently, the flame-formed beads having diameters between 180 micrometers and 250 micrometers were sprayed through a plasma gun and deposited on stainless and carbon steel substrates as described in Example 1.

[0168] The 1080 carbon steel substrates were flexed, thus separating the coating from the substrate resulting in a free-standing bulk material. The resulting bulk material had a z dimension (thickness) of about 700 micrometers, as determined using optical microscopy. The microstructure was also observed using optical microscopy. The material consisted of generally spherical and oblique crystalline particles, which were opaque, within a predominantly amorphous matrix, which was transparent. Amorphous material is typically transparent due to the lack of light scattering centers such as crystal boundaries, while the crystalline particles show a crystalline structure and are opaque due to light scattering effects. The crystalline phases, determined by powder XRD analysis as described in Example 1, consisted of Zr_(0.4)Ce_(0.6)O₂ (cubic) and transitional Al₂O₃.

[0169] A second deposition experiment was carried out using the flame-formed beads having diameters less than 125 micrometers. The resulting coating had a z dimension (thickness) of about 1100 micrometers, as determined using optical microscopy. The microstructure was also observed using optical microscopy. This material had similar features (i.e., consisted of generally spherical and oblique crystalline particles within a predominantly amorphous matrix) to those of the material formed from beads having diameters between 180 micrometers and 250 micrometers. The crystalline phases, determined by XRD analysis as described in Example 1, consisted of Zr_(0.4)Ce_(0.6)O₂ (cubic) and transitional Al₂O₃.

[0170] The average hardness of the as-sprayed material of this example was determined as follows. Sections of the material were mounted in mounting resin (obtained under the trade designation “TRANSOPTIC POWDER” from Buehler, Lake Bluff, Ill.). The resulting cylinder of resin was about 2.5 cm in diameter and about 1.9 cm high. The mounted section was prepared using conventional polishing techniques using a polisher (obtained from Buehler, Lake Bluff, Ill. under the trade designation “ECOMET 3”). The sample was polished for about 3 minutes with a diamond wheel, followed by 5 minutes of polishing with each of 45, 30, 15, 9, 3, and 1-micrometer slurries. The microhardness measurements were made using a conventional microhardness tester (obtained under the trade designation “MITUTOYO MVK-VL” from Mitutoyo Corporation, Tokyo, Japan) fitted with a Vickers indenter using a 100-gram indent load. The microhardness measurements were made according to the guidelines stated in ASTM Test Method E384 Test Methods for Microhardness of Materials (1991), the disclosure of which is incorporated herein by reference. The average microhardness (an average of 20 measurements) of the material of this example was 15 gigapascals (Gpa).

Example 3

[0171] Feed particles were made as described in Example 1 using the following 50-gram mixture: 27.9 grams of alumina particles (obtained from Alcoa Industrial Chemicals, Bauxite, Ark. under the trade designation “A16SG”), 7.8 grams of zirconium oxide particles (obtained from Zirconia Sales, Inc. of Marietta, Ga. under the trade designation “DK-2”), and 14.3 grams of yttrium oxide particles (obtained from H. C. Stark Newton, Mass.). The ratio of alumina to zirconia of initial starting materials was 3.5:1 and the alumina and zirconia collectively made up about 72 weight percent. The feed particles were then screened through a 30-mesh screen (600-micrometer opening size) and heat-treated at 1400° C. for 2 hours in an electrically heated furnace (obtained from CM Furnaces, Bloomfield, N.J. under the trade designation “Rapid Temp Furnace”). The heat-treated particles were further screened to separate out particles with diameters between 125 micrometers and 180 micrometers, which were then passed through a plasma gun and deposited on stainless steel substrates as described in Example 1.

[0172] The 1080 carbon steel substrate was flexed, thus separating the coating from the substrate resulting in a free-standing bulk material. The resulting bulk material had a z dimension (thickness) of about 700 micrometers, as determined using optical microscopy. The microstructure was observed using optical microscopy. This material consisted of generally crystalline opaque particles (which mostly retained their original angular shapes) within a predominantly transparent, amorphous matrix. The crystalline phases, determined by powder XRD analysis as described in Example 1, consisted of Al₅Y₃O₁₂ and Y_(0.15)Zr_(0.85)O_(1.93).

[0173] Another portion of the free-standing bulk material was crystallized at 1300° C. for 1 hour and the fractured surface was sputter coated with a thin layer of gold-palladium and viewed using a JEOL SEM (Model JSM 840A), as described above in Example 1. The fractured surface was rough and no crystals coarser than 200 nm were observed (see FIG. 5).

[0174] A second deposition experiment was carried out using heat-treated particles having diameters less than 125 micrometers. The resulting coating was about 1500 micrometers thick (z dimension). The microstructure was observed using optical microscopy. This material had similar features (consisted of generally opaque, crystalline particles (which mostly retained their original angular shapes) within a predominantly transparent, amorphous matrix) to the material formed from beads having diameters between 180 micrometers and 250 micrometers. The crystalline phases, determined by XRD analysis as described in Example 1, consisted of Al₅Y₃O₁₂ and Y_(0.15)Zr_(0.85)O_(1.93).

Example 4

[0175] A thick coating consisting of various layers of the above three examples was plasma sprayed using feed particles produced in Examples 1-3. The first layer was coated as described in Example 2, the second as described in Example 1, and the third as described in Example 3.

[0176] The substrate was not sandblasted prior to coating so that it was removed easily by plying it apart by hand, resulting in a free-standing bulk material, approximately 75 millimeters (mm)×25 mm×7.5 mm. A cross-section, cutting through each layer, was sectioned from the material using a diamond saw. The sectioned piece was mounted in mounting resin (obtained under the trade designation “TRANSOPTIC POWDER” from Buehler, Lake Bluff, 1L) such that the different layers were visible. The resulting cylinder of resin was about 2.5 cm in diameter and about 1.9 cm tall (i.e., high). The mounted section was prepared using conventional polishing techniques using a polisher (obtained from Buehler, Lake Bluff, Ill. under the trade designation “ECOMET 3”). The sample was polished for about 3 minutes with a diamond wheel, followed by 5 minutes of polishing with each of 45, 30, 15, 9, 3, and 1-micrometer slurries.

[0177] The first layer had a z dimension (thickness) of approximately 2.5 mm, as determined using optical microscopy. The microstructure was observed using optical microscopy. This material had similar features to those of the material of Example 2 (i.e., consisted of generally spherical and opaque crystalline particles within a predominantly transparent, amorphous matrix). The second layer had a z dimension (thickness) of approximately 2 mm, as determined using optical microscopy. The microstructure was also observed using optical microscopy. This material had similar features to those of the material of Example 1 (i.e., was transparent suggesting it was amorphous). The third layer had a z dimension (thickness) of approximately 3 mm, as determined using optical microscopy. The microstructure was also observed using optical microscopy. This material had similar features to those of the material of Example 3 (i.e., it consisted of generally opaque crystalline particles (which mostly retained their original angular shapes) within a predominantly transparent, amorphous matrix).

Examples 5-7

[0178] Feed particles were made as described in Example 1, except the mixtures used were those listed in Table 1, below, with the raw material sources listed in Table 2, below. Feed particles were flame formed into beads as described in Example 1.

[0179] A percent amorphous yield was calculated from the resulting flame-formed beads using a −100+120 mesh size fraction (i.e., the fraction collected between 150-micrometer opening size and 125-micrometer opening size screens). The measurements were done in the following manner. A single layer of beads was spread out upon a glass slide. The beads were observed using an optical microscope. Using the crosshairs in the optical microscope eyepiece as a guide, beads that lay along a straight line were counted either amorphous or crystalline depending on their optical clarity. A total of 500 beads were counted and a percent amorphous yield was determined by the amount of amorphous beads divided by total beads counted. For the examples, DTA was conducted as described in Example 1. The T_(g) and T_(x) values for certain examples are reported in Table 1, below. TABLE 1 Weight Percent Glass transition/ Batch percent of amorphous crystallization Example amounts, g components yield temperatures Ex. 5 Al₂O₃: 19.3 Al₂O₃: 38.5 La₂O₃: 21.2 La₂O₃: 42.5 882° C. ZrO₂: 9.5 ZrO₂: 19.0 98 932° C. Ex. 6 Al₂O₃: 20.5 Al₂O₃: 41.0 Gd₂O₃: 20.5 Gd₂O₃: 41.0 872° C. ZrO₂: 9 ZrO₂: 18 94 932° C. Ex. 7 Al₂O₃: 16.7 Al₂O₃: 33.3 Al: 8.8 Al: 17.6 Y₂O₃: 16 Y₂O₃: 31.9 900° C. ZrO₂: 8.6 ZrO₂: 17.2 89 935° C.

[0180] TABLE 2 Raw Material Source Alumina particles Obtained from Alcoa Industrial Chemicals, (Al₂O₃) Bauxite, AR, under the trade designation “Al6SG” Aluminum particles (Al) Obtained from Alfa Aesar, Ward Hill, MA Lanthanum oxide Obtained from Molycorp Inc., Mountain Pass, particles (La₂O₃) CA and calcined at 700° C. for 6 hours prior to batch mixing Gadolinium oxide Obtained from Molycorp Inc., Mountain Pass, particles (Gd₂O₃) CA Yttrium oxide particles Obtained from H. C. Stark Newton, MA (Y₂O₃) Zirconium oxide particles Obtained from Zirconia Sales, Inc. of Marietta, (ZrO₂) GA under the trade designation “DK-2”

[0181] About 25 grams of the beads from Example 5 were placed in a graphite die and hot-pressed using a uniaxial pressing apparatus (obtained under the trade designation “HP-50”, Thermal Technology Inc., Brea, Calif.). The hot pressing was carried out in an argon atmosphere and 13.8 megapascals (MPa) (2000 pounds per square inch or 2 ksi) pressure. The hot pressing furnace was ramped up to 970° C. at 25° C./minute. The resulting transparent disk, approximately 34 mm in diameter, 6 mm in thickness, was crushed by using a “Chipmunk” jaw crusher (Type VD, manufactured by BICO Inc., Burbank, Calif.) into abrasive particles and graded to retain the −30+35 fraction (i.e., the fraction collected between 600-micrometer opening size and 500-micrometer opening size screens) and the −35+40 mesh fraction (i.e., the fraction collected between 500-micrometer opening size and 425-micrometer opening size screens). The graded abrasive particles were crystallized by heat-treating at 1300° C. for 45 minutes in an electrically heated furnace. The crystalline phases, determined by XRD analysis as described in Example 1, included LaAlO₃, ZrO₂ (cubic, tetragonal), LaAl₁₁O₁₈, and transitional Al₂O₃ phases.

[0182] A second hot press disk of the material prepared in Example 5 was made as described above. The disk was crystallized by heat-treating at 1300° C. for 45 minutes in an electrically heated furnace. The crystalline phases, determined by XRD analysis as described in Example 1, included LaAlO₃, ZrO₂ (cubic, tetragonal), LaAl₁₁O₁₈, and transitional Al₂O₃ phases. The crystallized disk was crushed by using a “Chipmunk” jaw crusher (Type VD, manufactured by BICO Inc., Burbank, CA) into abrasive particles and graded to retain the −30+35 fraction (i.e., the fraction collected between 600-micrometer opening size and 500-micrometer opening size screens) and the −35+40 mesh fraction (i.e., the fraction collected between 500-micrometer opening size and 425-micrometer opening size screens).

[0183] The average microhardness of the heat-treated, graded particles was measured by mounting the particles in mounting resin (obtained under the trade designation “EPOMET” from Buehler Ltd., Lake Bluff, Ill.). The resulting cylinder of resin was about 2.5 cm (1 inch) in diameter and about 1.9 cm (0.75 inch) high. The mounted samples were polished using a conventional grinder/polisher (obtained under the trade designation “EPOMET” from Buehler Ltd.) and conventional diamond slurries with the final polishing step using a 1 micrometer diamond slurry (obtained under the trade designation “METADI” from Buehler Ltd.) to obtain polished cross-sections of the sample. The microhardness measurements were made using a conventional microhardness tester (obtained under the trade designation “MITUTOYO MVK-VL” from Mitutoyo Corporation, Tokyo, Japan) fitted with a Vickers indenter using a 500-gram indent load. The microhardness measurements were made according to the guidelines stated in ASTM Test Method E384 Test Methods for Microhardness of Materials (1991), the disclosure of which is incorporated herein by reference. The microhardness values were an average of 20 measurements. The average microhardness of the particles was 17.6 GPa.

Example 8

[0184] About 150 grams of the beads prepared as described in Example 5 were placed in a 5 centimeter (cm)×5 cm×5 cm steel can, which was then evacuated and sealed from the atmosphere. The steel can was subsequently hot-isostatically pressed (HIPed) using a HIP apparatus (obtained under the trade designation “IPS Eagle-6”, American Isostatic Pressing, OH). The HIPing was carried out at 207 MPa (30 ksi) pressure in an argon atmosphere. The HIPing furnace was ramped up to 970° C. at 25C/minute and held at that temperature for 30 minutes. After the HIPing, the steel can was cut and the charge material removed. It was observed that beads coalesced into a chunk of transparent, glassy material. The DTA trace, conducted as described in Example 1, exhibited a glass transition (T_(g)) of 879° C. and a crystallization temperature (T_(x)) of 931° C.

Examples 9-19

[0185] A 250-ml polyethylene bottle (7.3-cm diameter) was charged with a 50-gram mixture of various powders (as shown below in Table 3, below, with sources of the raw materials listed in Table 4, below), 75 grams of isopropyl alcohol, and 200 grams of alumina milling media (cylindrical shape, both height and diameter of 0.635 cm; 99.9% alumina; obtained from Coors, Golden, Colo.). The contents of the polyethylene bottle were milled for 16 hours at 60 revolutions per minute (rpm). After the milling, the milling media were removed and the slurry was poured onto a warm (approximately 75° C.) glass (“PYREX”) pan and dried. The dried mixture was screened through a 70-mesh screen (212-micrometer opening size) with the aid of a paint brush.

[0186] After grinding and screening, the mixture of milled feed particles was fed slowly (0.5 gram/minute) into a hydrogen/oxygen torch flame to melt the particles. The torch used to melt the particles, thereby generating molten droplets, was a Bethlehem bench burner PM2D Model B obtained from Bethlehem Apparatus Co., Hellertown, Pa. Hydrogen and oxygen flow rates for the torch were as follows. For the inner ring, the hydrogen flow rate was 8 standard liters per minute (SLPM) and the oxygen flow rate was 3.5 SLPM. For the outer ring, the hydrogen flow rate was 23 SLPM and the oxygen flow rate was 12 SLPM. The dried and sized particles were fed slowly (0.5 gram/minute) into the torch flame which melted the particles and carried them into a 19-liter (5-gallon) cylindrical container (30 cm diameter by 34 cm height) of continuously circulating, turbulent water to rapidly quench the molten droplets. The angle at which the flame hit the water was approximately 45°, and the flame length, burner to water surface, was approximately 18 centimeters (cm). The resulting molten and rapidly quenched particles were collected and dried at 110° C. The particles were spherical in shape and varied in size from a few micrometers (i.e., microns) up to 250 micrometers.

[0187] For certain examples, a percent amorphous yield was calculated as described in Examples 5-7. For certain examples, DTA was conducted as described in Example 1. The T_(g) and T_(x) values for certain examples are reported in Table 3, below.

[0188] Materials prepared in Examples 15 through 22 were amorphous as determined by visual inspection using optical microscopy. Quantitative analysis according to the above procedure was not performed. TABLE 3 Percent final Percent Glass transition/ Batch Weight percent Final weight alumina from Al amorphous crystallization Example amounts, g of components percent alumina % metal yield temperatures Ex. 9 Al₂O₃: 15.5 Al₂O₃: 31.0 AZ-Ti Al: 8.2 Al: 16.4 ZrO₂: 22.0 ZrO₂: 44.0 none TiO₂: 4.3 TiO₂: 8.6 54 50 79 936° C. Ex. 10 Al₂O₃: 12.3 Al₂O₃: 24.5 AZ-La Al: 6.5 Al: 13.0 ZrO₂: 17.4 ZrO₂: 34.8 889° C. La₂O₃: 13.8 La₂O₃: 27.7 44 50 94 918° C. Ex. 11 Al₂O₃: 9.1 Al₂O₃: 18.2 AZ-La Al: 4.8 Al: 9.6 ZrO₂: 13.0 ZrO₂: 25.9 868° C. La₂O₃: 23.1 La₂O₃: 46.2 34 50 96 907° C. Ex. 12 Al₂O₃: 7.5 Al₂O₃: 15.0 28 50 93 870° C. AZ-La Al: 4.0 Al: 8.0 898° C. ZrO₂: 17.0 ZrO₂: 34.0 La₂O₃21.4 La₂O₃42.8 Ex. 13 Al₂O₃: 17.87 Al₂O₃: 35.73 ALZ/ La₂O₃: 21.08 La₂O₃: 42.17 P₂O₅ ZrO₂: 8.55 ZrO₂: 17.1 P₂O₅: 2.5 P₂O₅: 5 857° C. 35.73 0  NA* 932° C. Ex. 14 Al₂O₃: 17.87 Al₂O₃: 35.73 ALZ/ La₂O₃: 21.08 La₂O₃: 42.17 Nb₂O₅ ZrO₂: 8.55 ZrO₂: 17.1 Nb₂O₅: 2.5 Nb₂O₅: 5 35.73 0 NA NA Ex. 15 Al₂O₃: 17.87 Al₂O₃: 35.73 ALZ/ La₂O₃: 21.08 La₂O₃: 42.17 Ta₂O₅ ZrO₂: 8.55 ZrO₂: 17.1 Ta₂O₅: 2.5 Ta₂O₅: 5 35.73 0 NA NA Ex. 16 Al₂O₃: 17.87 Al₂O₃: 35.73 ALZ/ La₂O₃: 21.08 La₂O₃: 42.17 SrO ZrO₂: 8.55 ZrO₂: 17.1 SrO: 2.5 SrO: 5 35.73 0 NA NA Ex. 17 Al₂O₃: 17.87 Al₂O₃: 35.73 ALZ/ La₂O₃: 21.08 La₂O₃: 42.17 Mn₂O₃ ZrO₂: 8.55 ZrO₂: 17.1 Mn₂O₃: 2.5 Mn₂O₃: 5 35.73 0 NA NA Ex. 18 Al₂O₃: 18.25 Al₂O₃: 36.5 ALZ/ La₂O₃: 21.52 La₂O₃: 43.04 Fe₂O₃ ZrO₂: 8.73 ZrO₂: 17.46 Fe₂O₃: 1.5 Fe₂O₃: 3 NA 36.5 0 NA Ex. 19 Al₂O₃: 18.25 Al₂O₃: 36.5 ALZ/ La₂O₃: 21.52 La₂O₃: 43.04 Cr₂O₃ ZrO₂: 8.73 ZrO₂: 17.46 Cr₂O₃: 1.5 Cr₂O₃: 3 36.5 0 NA NA

[0189] TABLE 4 Raw Material Source Alumina particles (Al₂O₃) Obtained from Alcoa Industrial Chemicals, Bauxite, AR, under the trade designation “Al6SG” Aluminum particles (Al) Obtained from Alfa Aesar, Ward Hill, MA Lanthanum oxide particles (La₂O₃) Obtained from Molycorp Inc., Mountain Pass, CA and calcined at 700° C. for 6 hours prior to batch mixing Titanium oxide particles (TiO₂) Obtained from Kemira, Savannah, GA, under the trade designation “UNITANE 0-110” Zirconium oxide particles (ZrO₂) Obtained from Zirconia Sales, Inc. of Marietta, GA under the trade designation “DK-2” Phosphorous oxide particles (P₂O₅) Obtained from Aldrich Chemical Co., Milwaukee, WI Niobium oxide particles (Nb₂O₅) Obtained from Aldrich Chemical Co. Tantalum oxide particles (Ta₂O₅) Obtained from Aldrich Chemical Co. Strontium oxide particles (SrO) Obtained from Aldrich Chemical Co. Manganese oxide particles (Mn₂O₃) Obtained from Aldrich Chemical Co. Iron oxide particles (Fe₂O₃) Obtained from Aldrich Chemical Co. Chromium oxide particles (Cr₂O₃) Obtained from Aldrich Chemical Co.

Examples 20-21

[0190] A 250-ml polyethylene bottle (7.3-cm diameter) was charged with 19.3 grams of alumina particles (obtained from Alcoa Industrial Chemicals, Bauxite, Ark., under the trade designation “A16SG”), 9.5 grams of zirconium oxide particles (obtained from Zirconia Sales, Inc. of Marietta, Ga. under the trade designation “DK-2”), and 21.2 grams of lanthanum oxide particles (obtained from Molycorp Inc., Mountain Pass, Calif.), 75 grams of isopropyl alcohol, and 200 grams of alumina milling media (cylindrical shape, both height and diameter of 0.635 cm; 99.9% alumina; obtained from Coors, Golden, Colo.). The contents of the polyethylene bottle were milled for 16 hours at 60 revolutions per minute (rpm). After the milling, the milling media were removed and the slurry was poured onto a warm (approximately 75° C.) glass (“PYREX”) pan, where it dried within 3 minutes. The dried mixture was screened through a 14-mesh screen (1400 micrometer opening size) with the aid of a paint brush and pre-sintered at 1400° C., in air, for two hours.

[0191] A hole (approximately 13 mm in diameter, about 8 cm deep) was bored at the end of a graphite rod (approximately 60 cm long, 15 mm in diameter). About 20 grams of pre-sintered particles were inserted into the hollow end. The hollow end of the graphite rod was inserted into the hot zone of a resistively heated furnace (obtained from Astro Industries, Santa Barbara, Calif.). The furnace was modified to convert it into a tube furnace with graphite tube with an inner diameter of approximately 18 mm. The hot zone was maintained at a temperature of 2000° C. and the furnace was tilted approximately 30° so that the melt would not spill out of the rod. The hallow end of the rod was held in the hot zone for 10 minutes to ensure uniform melting. After the ten minutes, the rod was quickly removed from the furnace and tilted to pour the melt onto a quenching surface.

[0192] For Example 20, the quenching surface was two opposing stainless steel plates. The plates, 17.8 cm×5 cm×2.5 cm, were placed on their long edges parallel to each other with a gap of about 1 mm. The melt was poured into the gap where it rapidly solidified into a plate with a z dimension (thickness) of about 1 mm. The quenched melt was predominantly transparent and amorphous and exhibited a glass transition (T_(g)) of 885° C. and a crystallization temperature (T_(x)) of 930° C. as determine by a DTA trace obtained as described in Example 1.

[0193] For Example 21, the quenching surface was two counter-rotating steel rollers. Rollers were 5 cm in diameter and driven by an electric motor at 80 rpm. The gap between the rollers was approximately 0.8 mm. The melt was poured into the gap where the rollers rapidly solidified into a plate with significant x and y dimensions and a z dimension (thickness) of 0.8 mm. The quenched melt was predominantly transparent and amorphous and exhibited a glass transition (T_(g)) of 885° C. and a crystallization temperature (T_(x)) of 930° C., as determine by a DTA trace obtained as described in Example 1.

Example 22

[0194] A polyethylene bottle was charged with 27.5 grams of alumina particles (obtained under the trade designation “APA-0.5” from Condea Vista, Tucson, Ariz.), 22.5 grams of calcium oxide particles (obtained from Alfa Aesar, Ward Hill, Mass.) and 90 grams of isopropyl alcohol. About 200 grams of zirconia milling media (obtained from Tosoh Ceramics, Division of Bound Brook, N.J., under “YTZ” designation) were added to the bottle, and the mixture was milled at 120 revolutions per minute (rpm) for 24 hours. After the milling, the milling media were removed and the slurry was poured onto a glass (“PYREX”) pan where it was dried using a heat-gun. The dried mixture was ground with a mortar and pestle and screened through a 70-mesh screen (212-micrometer opening size).

[0195] After grinding and screening, some of the particles were fed into a hydrogen/oxygen torch flame. The torch used to melt the particles, thereby generating melted glass beads, was a Bethlehem bench burner PM2D model B, obtained from Bethlehem Apparatus Co., Hellertown, Pa., delivering hydrogen and oxygen at the following rates. For the inner ring, the hydrogen flow rate was 8 standard liters per minute (SLPM) and the oxygen flow rate was 3 SLPM. For the outer ring, the hydrogen flow rate was 23 (SLPM) and the oxygen flow rate was 9.8 SLPM. The dried and sized particles were fed directly into the torch flame, where they were melted and transported to an inclined stainless steel surface (approximately 51 centimeters (cm) (20 inches) wide with the slope angle of 45 degrees) with cold water running over (approximately 8 liters/minute) the surface to form amorphous beads.

Examples 23 and 24

[0196] Examples 23-24 glass beads were prepared as described in Example 22, except the raw materials and the amounts of raw materials used are listed in Table 5, below, and the milling of the raw materials was carried out in 90 (milliliters) ml of isopropyl alcohol with 200 grams of the zirconia media (obtained from Tosoh Ceramics, Division of Bound Brook, N.J., under “YTZ” designation) at 120 rpm for 24 hours. The sources of the raw materials used are listed in Table 6, below. TABLE 5 Example Weight percent of components Batch amounts, g 23 CaO: 36 CaO: 18 Al₂O₃: 44 Al₂O₃: 22 ZrO₂: 20 ZrO₂: 10 24 La₂O₃: 40.9 La₂O₃: 20.45 Al₂O₃: 40.98 Al₂O₃: 20.49 ZrO₂: 18.12 ZrO₂: 9.06

[0197] TABLE 6 Raw Material Source Alumina particles (Al₂O₃) Obtained from Condea Vista, Tucson, AZ under the trade designation “APA-0.5” Calcium oxide particles (CaO) Obtained from Alfa Aesar, Ward Hill, MA Lanthanum oxide particles Obtained from Molycorp Inc. (La₂O₃) Yttria-stabilized zirconium Obtained from Zirconia Sales, Inc. of oxide particles (Y-PSZ) Marietta, GA under the trade designation “HSY-3”

[0198] Various properties/characteristics of some of Examples 22-24 materials were measured as follows. Powder X-ray diffraction (using an X-ray diffractometer (obtained under the trade designation “PHILLIPS XRG 3100” from PHILLIPS, Mahwah, N.J.) with copper K α1 radiation of 1.54050 Angstrom)) was used to qualitatively measure phases present in example materials. The presence of a broad diffused intensity peak was taken as an indication of the amorphous nature of a material. The existence of both a broad peak and well-defined peaks was taken as an indication of existence of crystalline matter within an amorphous matrix. Phases detected in various examples are reported in Table 7, below. TABLE 7 Phases detected via Hot-pressing Example X-ray diffraction Color T_(g), ° C. T_(x), ° C. temp, ° C. 22 Amorphous* Clear 850 987 985 23 Amorphous* Clear 851 977 975 24 Amorphous* Clear 839 932 965

[0199] For differential thermal analysis (DTA), a material was screened to retain glass beads within the 90-125 micrometer size range. DTA runs were made (using an instrument obtained from Netzsch Instruments, Selb, Germany under the trade designation “NETZSCH STA 409 DTA/TGA”). The amount of each screened sample placed in a 100-microliter Al₂O₃ sample holder was 400 milligrams. Each sample was heated in static air at a rate of 10° C./minute from room temperature (about 25° C.) to 1200° C.

[0200] Referring to FIG. 6, line 345 is the plotted DTA data for the Example 22 material. Referring to FIG. 6 line 345, the material exhibited an endothermic event at a temperature around 799° C., as evidenced by the downward curve of line 375. It was believed that this event was due to the glass transition (T_(g)) of the material. At about 875° C., an exothermic event was observed as evidenced by the sharp peak in line 345. It was believed that this event was due to the crystallization (T_(x)) of the material. These T_(g) and T_(x) values for other examples are reported in Table 7, above.

[0201] FIGS. 7-8 are the plotted DTA data for Examples 23 and 24, respectively.

[0202] For each of Examples 22-24, about 25 grams of the glass beads were placed in a graphite die and hot-pressed using uniaxial pressing apparatus (obtained under the trade designation “HP-50”, Thermal Technology Inc., Brea, Calif.). The hot-pressing was carried out in an argon atmosphere and 13.8 megapascals (MPa) (2000 pounds per square inch (2 ksi)) pressure. The hot-pressing temperature at which appreciable glass flow occurred, as indicated by the displacement control unit of the hot pressing equipment described above, are reported for Examples 22-24 in Table 7, above.

Examples 25-31

[0203] A polyethylene bottle was charged with the raw materials listed in Table 8, below (with the sources of the raw materials listed in Table 9, below), with 90 ml of isopropyl alcohol. About 200 grams of the zirconia milling media (obtained from Tosoh Ceramics, Division of Bound Brook, N.J., under the trade designation “YTZ”) were added to the bottle, and the mixture was milled at 120 revolutions per minute (rpm) for 24 hours. After the milling, the milling media were removed and the slurry was poured onto a glass (“PYREX”) pan where it was dried using a heat-gun. The dried mixture was ground with a mortar and pestle and screened through a 70-mesh screen (212-micrometer opening size screen). After grinding and screening, some of the particles were fed into a hydrogen/oxygen torch flame to form beads as described in Example 1. TABLE 8 Example Weight percent of components Batch amounts, g 25 Y₂O₃: 28.08 Y₂O₃: 14.04 Al₂O₃: 58.48 Al₂O₃: 29.24 ZrO₂: 13.43 ZrO₂: 6.72 26 Y₂O₃: 19 Y₂O₃: 9.5 Al₂O₃: 51 Al₂O₃: 25.5 ZrO₂: 17.9 ZrO₂: 8.95 La₂O₃: 12.1 La₂O₃: 6.05 27 Y₂O₃: 19.3 Y₂O₃: 9.65 Al₂O₃: 50.5 Al₂O₃: 25.25 ZrO₂: 17.8 ZrO₂: 8.9 Nd₂O₃: 12.4 Nd₂O₃: 6.2 28 Y₂O₃: 27.4 Y₂O₃: 13.7 Al₂O₃: 50.3 Al₂O₃: 25.15 ZrO₂: 17.8 ZrO₂: 8.9 Li₂CO₃: 4.5 Li₂CO₃: 2.25 29 Y₂O₃: 27.4 Y₂O₃: 13.7 Al₂O₃: 50.3 Al₂O₃: 25.15 ZrO₂: 17.8 ZrO₂: 8.9 CaO: 4.5 CaO: 2.25 30 Y₂O₃: 27.4 Y₂O₃: 13.7 Al₂O₃: 50.3 Al₂O₃: 25.15 ZrO₂: 17.8 ZrO₂: 8.9 NaHCO₃: 2.25 NaHCO₃: 2.25 31 Y₂O₃: 27.4 Y₂O₃: 13.7 Al₂O₃: 50.3 Al₂O₃: 25.15 ZrO₂: 17.8 ZrO₂: 8.9 SiO₂: 2.25 SiO₂: 2.25

[0204] TABLE 9 Raw Material Source Alumina particles (Al₂O₃) Obtained from Condea Vista, Tucson, AZ under the trade designation “APA-0.5” Calcium oxide particles (CaO) Obtained from Alfa Aesar, Ward Hill, MA Lanthanum oxide particles Obtained from Molycorp Inc., Mountain (La₂O₃) Pass, CA Lithium carbonate particles Obtained from Aldrich Chemical Co. (Li₂CO₃) Neodymium oxide particles Obtained from Molycorp Inc. (Nd₂O₃) Silica particles (SiO₂) Obtained from Alfa Aesar Sodium bicarbonate particles Obtained from Aldrich Chemical Co. (NaHCO₃) Yttria-stabilized zirconium Obtained from Zirconia Sales, Inc. of oxide particles (Y-PSZ) Marietta, GA under the trade designation “HSY-3”

[0205] Various properties/characteristics of some Example 25-31 materials were measured as follows. Powder X-ray diffraction (using an X-ray diffractometer (obtained under the trade designation “PHILLIPS XRG 3100” from Phillips, Mahwah, N.J.) with copper K α1 radiation of 1.54050 Angstrom)) was used to qualitatively measure phases present in example materials. The presence of a broad diffused intensity peak was taken as an indication of the amorphous nature of a material. The existence of both a broad peak and well-defined peaks was taken as an indication of existence of crystalline matter within an amorphous matrix. Phases detected in various examples are reported in Table 10, below. TABLE 10 Phases Hot- Exam- detected via pressing ple X-ray diffraction Color T_(g), ° C. T_(x), ° C. temp, ° C. 25 Amorphous* and Clear/milky 874 932 980 Crystalline 26 Amorphous* Clear 843 938 970 27 Amorphous* Blue/pink 848 934 970 28 Amorphous* Clear 821 927 970 29 Amorphous* Clear 845 922 970 30 Amorphous* Clear 831 916 970 31 Amorphous* Clear 826 926 970

[0206] For differential thermal analysis (DTA), a material was screened to retain beads in the 90-125 micrometer size range. DTA runs were made (using an instrument obtained from Netzsch Instruments, Selb, Germany under the trade designation “NETZSCH STA 409 DTA/TGA”). The amount of each screened sample placed in a 100-microliter Al₂O₃ sample holder was 400 milligrams. Each sample was heated in static air at a rate of 10° C./minute from room temperature (about 25° C.) to 1200° C.

[0207] The hot-pressing temperature at which appreciable glass flow occurred, as indicated by the displacement control unit of the hot pressing equipment described above, are reported for various examples in Table 10, above.

Example 32

[0208] A polyurethane-lined mill was charged with 819.6 grams of alumina particles (“APA-0.5”), 818 grams of lanthanum oxide particles (obtained from Molycorp, Inc.), 362.4 grams of yttria-stabilized zirconium oxide particles (with a nominal composition of 94.6 wt-% ZrO₂ (+HfO₂) and 5.4 wt-% Y₂O₃; obtained under the trade designation “HSY-3” from Zirconia Sales, Inc. of Marietta, Ga.), 1050 grams of distilled water and about 2000 grams of zirconia milling media (obtained from Tosoh Ceramics, Division of Bound Brook, N.J., under the trade designation “YTZ”). The mixture was milled at 120 revolutions per minute (rpm) for 4 hours to thoroughly mix the ingredients. After the milling, the milling media were removed and the slurry was poured onto a glass (“PYREX”) pan where it was dried using a heat-gun. The dried mixture was ground with a mortar and pestle and screened through a 70-mesh screen (212-micrometer opening size). After grinding and screening, some of the particles were fed into a hydrogen/oxygen torch flame as described in Example 1.

[0209] About 50 grams of the beads was placed in a graphite die and hot-pressed using a uniaxial pressing apparatus (obtained under the trade designation “HP-50”, Thermal Technology Inc., Brea, Calif.). The hot-pressing was carried out at 960° C. in an argon atmosphere and 13.8 megapascals (MPa) (2000 pounds per square inch (2 ksi)) pressure. The resulting translucent disk was about 48 millimeters in diameter, and about 5 mm thick. Additional hot-press runs were performed to make additional disks. FIG. 9 is an optical photomicrograph of a sectioned bar (2-mm thick) of the hot-pressed material demonstrating its transparency.

[0210] The density of the resulting hot-pressed glass material was measured using Archimedes method, and found to be within a range of about 4.1-4.4 g/cm³. The Youngs' modulus (E) of the resulting hot-pressed glass material was measured using a ultrasonic test system (obtained from Nortek, Richland, Wash. under the trade designation “NDT-140”), and found to be within a range of about 130-150 GPa.

[0211] The average microhardnesses of the resulting hot-pressed material was determined as follows. Pieces of the hot-pressed material (about 2-5 millimiters in size) were mounted in mounting resin (obtained under the trade designation “EPOMET” from Buehler Ltd., Lake Bluff, Ill.). The resulting cylinder of resin was about 2.5 cm (1 inch) in diameter and about 1.9 cm (0.75 inch) tall (i.e., high). The mounted samples were polished using a conventional grinder/polisher (obtained under the trade designation “EPOMET” from Buehler Ltd.) and conventional diamond slurries with the final polishing step using a 1-micrometer diamond slurry (obtained under the trade designation “METADI” from Buehler Ltd.) to obtain polished cross-sections of the sample.

[0212] The microhardness measurements were made using a conventional microhardness tester (obtained under the trade designation “MITUTOYO MVK-VL” from Mitutoyo Corporation, Tokyo, Japan) fitted with a Vickers indenter using a 500-gram indent load. The microhardness measurements were made according to the guidelines stated in ASTM Test Method E384 Test Methods for Microhardness of Materials (1991), the disclosure of which is incorporated herein by reference. The microhardness values were an average of 20 measurements. The average microhardness of the hot-pressed material was about 8.3 GPa.

[0213] The average indentation toughness of the hot-pressed material was calculated by measuring the crack lengths extending from the apices of the vickers indents made using a 500 gram load with a microhardness tester (obtained under the trade designation “MITUTOYO MVK-VL” from Mitutoyo Corporation, Tokyo, Japan). Indentation toughness (K_(IC)) was calculated according to the equation:

K _(IC)=0.016(E/H)^(1/2)(P/c)^(3/2)

[0214] wherein: E=Young's Modulus of the material;

[0215] H=Vickers hardness;

[0216] P=Newtons of force on the indenter;

[0217] c=Length of the crack from the center of the indent to its end.

[0218] Samples for the toughness were prepared as described above for the microhardness test. The reported indentation toughness values are an average of 5 measurements. Crack (c) were measured with a digital caliper on photomicrographs taken using a scanning electron microscope (“JEOL SEM” (Model JSM 6400)). The average indentation toughness of the hot-pressed material was 1.4 MPa.m^(1/2). The thermal expansion coefficient of the hot-pressed material was measured using a thermal analyser (obtained from Perkin Elmer, Shelton, Conn., under the trade designation “PERKIN ELMER THERMAL ANALYSER”). The average thermal expansion coefficient was 7.6×10⁻⁶/° C.

[0219] The thermal conductivity of the hot-pressed material was measured according to an ASTM standard “D 5470-95, Test Method A” (1995), the disclosure of which is incorporated herein by reference. The average thermal conductivity was 1.15 W/m*K.

[0220] The translucent disk of hot-pressed La₂O₃—Al₂O₃—ZrO₂ glass was heat-treated in a furnace (an electrically heated furnace (obtained under the trade designation “Model KKSK-666-3100” from Keith Furnaces of Pico Rivera, Calif.)) as follows. The disk was first heated from room temperature (about 25° C.) to about 900° C. at a rate of about 10° C./min and then held at 900° C. for about 1 hour. Next, the disk was heated from about 900° C. to about 1300° C. at a rate of about 10° C./min and then held at 1300° C. for about 1 hour, before cooling back to room temperature by turning off the furnace. Additional runs were performed with the same heat-treatment schedule to make additional disks.

[0221]FIG. 10 is a scanning electron microscope (SEM) photomicrograph of a polished section of heat-treated Example 32 material showing the fine crystalline nature of the material. The polished section was prepared using conventional mounting and polishing techniques. Polishing was done using a polisher (obtained from Buehler of Lake Bluff, Ill. under the trade designation “ECOMET 3 TYPE POLISHER-GRINDER”). The sample was polished for about 3 minutes with a diamond wheel, followed by three minutes of polishing with each of 45, 30, 15, 9, and 3-micrometer diamond slurries. The polished sample was coated with a thin layer of gold-palladium and viewed using JEOL SEM (Model JSM 840A).

[0222] Based on powder X-ray diffraction of a portion of heat-treated Example 32 material and examination of the polished sample using SEM in the backscattered mode, it is believed that the dark portions in the photomicrograph were crystalline LaAl₁₁O_(18,) the gray portions crystalline LaAlO₃, and the white portions crystalline cubic/tetragonal ZrO₂.

[0223] The density of the heat-treated material was measured using Archimedes method, and found to be about 5.18 g/cm³. The Youngs' modulus (E) of the heat-treated material was measured using an ultrasonic test system (obtained from Nortek, Richland, Wash. under the trade designation “NDT-140”), and found to be about 260 GPa. The average microhardness of the heat-treated material was determined as described above for the Example 32 glass beads, and was found to be 18.3 GPa. The average fracture toughness (K_(IC)) of the heat-treated material was determined as described above for the Example 32 hot-pressed material, and was found to be 3.3 MPa*m^(1/2).

Examples 33-49

[0224] Examples 33-49 beads were prepared as described in Example 32, except the raw materials and the amounts of raw materials, used are listed in Table 11, below, and the milling of the raw materials was carried out in 90 milliliters (ml) of isopropyl alcohol with 200 grams of the zirconia media (obtained from Tosoh Ceramics, Division of Bound Brook, NJ, under the trade designation “YTZ”) at 120 rpm for 24 hours. The sources of the raw materials used are listed in Table 12, below. TABLE 11 Weight percent of Example components Batch amounts, g 33 La₂O₃: 45.06 La₂O₃: 22.53 Al₂O₃: 34.98 Al₂O₃: 17.49 ZrO₂: 19.96 ZrO₂: 9.98 34 La₂O₃: 36.74 La₂O₃: 18.37 Al₂O₃: 46.98 Al₂O₃: 23.49 ZrO₂: 16.28 ZrO₂: 8.14 35 La₂O₃: 35.35 La₂O₃: 17.68 Al₂O₃: 48.98 Al₂O₃: 24.49 ZrO₂: 15.66 ZrO₂: 7.83 36 Al₂O₃: 41.0 Al₂O₃: 20.5 ZrO₂: 17.0 ZrO₂: 8.5 Eu₂O₃: 41.0 Eu₂O₃: 20.5 37 Al₂O₃: 41.0 Al₂O₃: 20.5 ZrO₂: 18.0 ZrO₂: 9.0 Gd₂O₃: 41.0 Gd₂O₃: 20.5 38 Al₂O₃: 41.0 Al₂O₃: 20.5 ZrO₂: 18.0 ZrO₂: 9.0 Dy₂O₃: 41.0 Dy₂O₃: 20.5 39 La₂O₃: 35.0 La₂O₃: 17.5 Al₂O₃: 40.98 Al₂O₃: 20.49 ZrO₂: 18.12 ZrO₂: 9.06 Nd₂O₃: 5.0 Nd₂O₃: 2.50 40 La₂O₃: 35.0 La₂O₃: 17.5 Al₂O₃: 40.98 Al₂O₃: 20.49 ZrO₂: 18.12 ZrO₂: 9.06 CeO₂: 5.0 CeO₂: 2.50 41 HfO₂: 35.5 HfO₂: 17.75 Al₂O₃: 32.5 Al₂O₃: 16.25 La₂O₃: 32.5 La₂O₃: 16.25 42 La₂O₃: 41.7 La₂O₃: 20.85 Al₂O₃: 35.4 Al₂O₃: 17.7 ZrO₂: 16.9 ZrO₂: 8.45 MgO: 6.0 MgO: 3.0 43 La₂O₃: 43.02 La₂O₃: 21.51 Al₂O₃: 36.5 Al₂O₃: 18.25 ZrO₂: 17.46 ZrO₂: 8.73 Li₂CO₃: 3.0 Li₂CO₃: 1.50 44 La₂O₃: 41.7 La₂O₃: 20.85 Al₂O₃: 35.4 Al₂O₃: 17.70 ZrO₂: 16.9 ZrO₂: 8.45 Li₂CO₃: 6.0 Li₂CO₃: 3.00 45 La₂O₃: 38.8 La₂O₃: 19.4 Al₂O₃: 40.7 Al₂O₃: 20.35 ZrO₂: 17.5 ZrO₂: 8.75 Li₂CO₃: 3 Li₂CO₃: 1.50 46 La₂O₃: 43.02 La₂O₃: 21.51 Al₂O₃: 36.5 Al₂O₃: 18.25 ZrO₂: 17.46 ZrO₂: 8.73 TiO₂: 3 TiO₂: 1.50 47 La₂O₃: 43.02 La₂O₃: 21.51 Al₂O₃: 36.5 Al₂O₃: 18.25 ZrO₂: 17.46 ZrO₂: 8.73 NaHCO₃: 3.0 NaHCO₃: 1.50 48 La₂O₃: 42.36 La₂O₃: 21.18 Al₂O₃: 35.94 Al₂O₃: 17.97 ZrO₂: 17.19 ZrO₂: 8.60 NaHCO₃: 4.5 NaHCO₃: 2.25 49 La₂O₃: 43.02 La₂O₃: 21.51 Al₂O₃: 36.5 Al₂O₃: 18.25 ZrO₂: 17.46 ZrO₂: 8.73 MgO: 1.5 MgO: 0.75 NaHCO₃: 1.5 NaHCO₃: 0.75 TiO₂: 1.5 TiO₂: 0.75

[0225] TABLE 12 Raw Material Source Alumina particles (Al₂O₃) Obtained from Condea Vista, Tucson, AZ under the trade designation “APA-0.5” Cerium oxide particles (CeO₂) Obtained from Rhone-Poulenc, France Europium oxide particles (Eu₂O₃) Obtained from Aldrich Chemical Co. Gadolinium oxide particles (Gd₂O₃) Obtained from Molycorp Inc., Mountain Pass, CA Hafnium oxide particles (HfO₂) Obtained from Teledyne Wah Chang Albany Co., Albany, OR Lanthanum oxide particles (La₂O₃) Obtained from Molycorp Inc. Lithium carbonate particles (Li₂CO₃) Obtained from Aldrich Chemical Co. Magnesium oxide particles (MgO) Obtained from Aldrich Chemical Co. Neodymium oxide particles (Nd₂O₃) Obtained from Molycorp Inc. Sodium bicarbonate particles (NaHCO₃) Obtained from Aldrich Chemical Co. Titanium dioxide particles (TiO₂) Obtained from Kemira Inc., Savannah, GA Yttria-stabilized zirconium oxide particles Obtained from Zirconia Sales, Inc. of (Y-PSZ) Marietta, GA under the trade designation “HSY-3”

[0226] Various properties/characteristics of some Example 32-49 materials were measured as follows. Powder X-ray diffraction (using an X-ray diffractometer (obtained under the trade designation “PHILLIPS XRG 3100” from PHILLIPS, Mahwah, N.J.) with copper K α1 radiation of 1.54050 Angstrom)) was used to qualitatively measure phases present in example materials. The presence of a broad diffused intensity peak was taken as an indication of the glassy nature of a material. The existence of both a broad peak and well-defined peaks was taken as an indication of existence of crystalline matter within a glassy matrix. Phases detected in various examples are reported in Table 13, below. TABLE 13 Phases detected Hot- via X-ray pressing Example diffraction Color T_(g), ° C. T_(x), ° C. temp, ° C. 32 Amorphous* Clear 834 932 960 33 Amorphous* Clear 837 936 960 34 Amorphous* Clear 848 920 960 35 Amorphous* Clear 856 918 960 36 Amorphous* Intense 874 921 975 yellow/ mustard 37 Amorphous* Clear 886 933 985 38 Amorphous* Greenish 881 935 985 39 Amorphous* Blue/pink 836 930 965 40 Amorphous* Yellow 831 934 965 41 Amorphous* Light green 828 937 960 42 Amorphous* Clear 795 901 950 43 Amorphous* Clear 816 942 950 44 Amorphous* Clear 809 934 950 45 Amorphous* Clear/ 840 922 950 greenish 46 Amorphous* Clear 836 934 950 47 Amorphous* Clear 832 943 950 48 Amorphous* Clear 830 943 950 49 Amorphous* Clear/some 818 931 950 green

[0227] For differential thermal analysis (DTA), a material was screened to retain beads in the 90-125 micrometer size range. DTA runs were made (using an instrument obtained for Netzsch Instruments, Selb, Germany under the trade designation “NETZSCH STA 409 DTA/TGA”). The amount of each screened sample placed in a 100-microliter Al₂O₃ sample holder was 400 milligrams. Each sample was heated in static air at a rate of 10° C./minute from room temperature (about 25° C.) to 1200° C.

[0228] Referring to FIG. 11, line 801 is the plotted DTA data for the Example 32 material. Referring to FIG. 11 line 801, the material exhibited an endothermic event at temperature around 840° C., as evidenced by the downward curve of line 801. It was believed that this event was due to the glass transition (T_(g)) of the material. At about 934° C., an exothermic event was observed as evidenced by the sharp peak in line 801. It was believed that this event was due to the crystallization (T_(x)) of the material. These T_(g) and T_(x) values for other examples are reported in Table 13, above.

[0229] The hot-pressing temperature at which appreciable glass flow occurred, as indicated by the displacement control unit of the hot pressing equipment described above, are reported for various examples in Table 13, above.

Example 50

[0230] A polyethylene bottle was charged with 20.49 grams of alumina particles (“APA-0.5”), 20.45 grams of lanthanum oxide particles (obtained from Molycorp, Inc.), 9.06 grams of yttria-stabilized zirconium oxide particles (with a nominal composition of 94.6 wt-% ZrO₂ (+HfO₂) and 5.4 wt-% Y₂O₃; obtained under the trade designation “HSY-3” from Zirconia Sales, Inc. of Marietta, Ga.), and 80 grams of distilled water. About 450 grams of alumina milling media (10 mm diameter; 99.9% alumina; obtained from Union Process, Akron, Ohio) were added to the bottle, and the mixture was milled at 120 revolutions per minute (rpm) for 4 hours to thoroughly mix the ingredients. After the milling, the milling media were removed and the slurry was poured onto a glass (“PYREX”) pan where it was dried using a heat-gun. The dried mixture was ground with a mortar and pestle and screened through a 70-mesh screen (212-micrometer opening size).

[0231] A small quantity of the dried particles was melted in an arc discharge furnace (Model No. 5T/A 39420; from Centorr Vacuum Industries, Nashua, N.H.). About 1 gram of the dried and sized particles was placed on a chilled copper plate located inside the furnace chamber. The furnace chamber was evacuated and then backfilled with Argon gas at 13.8 kilopascals (kPa) (2 pounds per square inch (psi)) pressure. An arc was struck between an electrode and a plate. The temperatures generated by the arc discharge were high enough to quickly melt the dried and sized particles. After melting was complete, the material was maintained in a molten state for about 10 seconds to homogenize the melt. The resultant melt was rapidly cooled by shutting off the arc and allowing the melt to cool on its own. Rapid cooling was ensured by the small mass of the sample and the large heat sinking capability of the water chilled copper plate. The fused material was removed from the furnace within one minute after the power to the furnace was turned off. Although not wanting to be bound by theory, it is estimated that the cooling rate of the melt on the surface of the water chilled copper plate was above 100° C./second. The fused material were transparent glass beads (largest diameter of a bead was measured at 2.8 millimeters (mm)).

[0232] The resulting amorphous beads were placed in a poyethylene bottle (as in Example 1) together with 200 grams of 2-mm zirconia milling media (obtained from Tosoh Ceramics Bound Brook, N.J. under the trade designation “YTZ”). Three hundred grams of distilled water was added to the bottle, and the mixture milled for 24 hours at 120 rpm to pulverize beads into powder. The milled material was dried using a heat gun. Fifteen grams of the dried particles were placed in a graphite die and hot-pressed at 960° C. as described in Examples 5-7. The resulting disk was translucent.

Example 51

[0233] Example 51 fused amorphous beads were prepared as described in Example 50. About 15 grams of the beads were hot pressed as described in Example 50 except the bottom punch of the graphite die had 2 mm deep grooves. The resulting material replicated the grooves, indicating very good flowability of the glass during the heating under the applied pressure.

Comparative Example A

[0234] Comparative Example A fused material was prepared as described in Example 50, except the polyethylene bottle was charged with 27 grams of alumina particles (“APA-0.5”), 23 grams of yttria-stabilized zirconium oxide particles (with a nominal composition of 94.6 wt-% ZrO₂ (+HfO₂) and 5.4 wt-% Y₂O₃; obtained under the trade designation “HSY-3” from Zirconia Sales, Inc. of Marietta, Ga.) and 80 grams of distilled water. The composition of this example corresponds to a eutectic composition in the Al₂O₃-ZrO₂ binary system. The resulting 100-150 micrometers diameter spheres were partially amorphous, with significant portions of crystallinity as evidenced by X-ray diffraction analysis.

Example 52

[0235] A sample (31.25 grams) of amorphous beads prepared as described in Example 32, and 18.75 grams of beads prepared as described in Comparative Example A, were placed in a polyethylene bottle. After 80 grams of distilled water and 300 grams of zirconia milling media (Tosoh Ceramics, Bound Brook, N.J. under the trade designation “YTZ”) were added to the bottle, the mixture was milled for 24 hours at 120 rpm. The milled material was dried using a heat gun. Twenty grams of the dried particles were hot-pressed as described in Example 32. An SEM photomicrograph of a polished section prepared as described in Example 32 of Example 32 material is shown in FIG. 12. The absence of cracking at interfaces between the Comparative Example A material (dark areas) and the Example 52 material (light areas) indicates the establishment of good bonding.

[0236] Grinding Performance of Examples 32 and 32A and Comparative Examples B-D

[0237] Example 32 hot-pressed material was crushed by using a “Chipmunk” jaw crusher (Type VD, manufactured by BICO Inc., Burbank, Calif.) into (abrasive) particles and graded to retain the −25+30 mesh fraction (i.e., the fraction collected between 25-micrometer opening and 30-micrometer opening size sieves) and −30+35 mesh fractions (i.e., the fraction collected between 30-micrometer opening size and 35-micrometer opening size sieves) (USA Standard Testing Sieves). These two mesh fractions were combined to provide a 50/50 blend. The blended material was heat treated as described in Example 32. Thirty grams of the resulting glass-ceramic abrasive particles were incorporated into a coated abrasive disc. The coated abrasive disc was made according to conventional procedures. The glass-ceramic abrasive particles were bonded to 17.8 cm diameter, 0.8 mm thick vulcanized fiber backings (having a 2.2 cm diameter center hole) using a conventional calcium carbonate-filled phenolic make resin (48% resole phenolic resin, 52% calcium carbonate, diluted to 81% solids with water and glycol ether) and a conventional cryolite-filled phenolic size resin (32% resole phenolic resin, 2% iron oxide,

[0238] 66% cryolite, diluted to 78% solids with water and glycol ether). The wet make resin weight was about 185 g/m². Immediately after the make coat was applied, the glass-ceramic abrasive particles were electrostatically coated. The make resin was precured for 120 minutes at 88° C. Then the cryolite-filled phenolic size coat was coated over the make coat and abrasive particles. The wet size weight was about 850 g/m². The size resin was cured for 12 hours at 99° C. The coated abrasive disc was flexed prior to testing.

[0239] Example 32A coated abrasive disk was prepared as described for Example 32 except the Example 32A abrasive particles were obtained by crushing a hot-pressed and heat-treated Example 32 material, rather than crushing then heat-treating.

[0240] Comparative Example B coated abrasive disks were prepared as described for Example 32 (above), except heat-treated fused alumina abrasive particles (obtained under the trade designation “ALODUR BFRPL”” from Triebacher, Villach, Austria) was used in place of the Example 32 glass-ceramic abrasive particles.

[0241] Comparative Example C coated abrasive discs were prepared as described for Example 32 (above), except alumina-zirconia abrasive particles (having a eutectic composition of 53% Al₂O₃ and 47% ZrO₂; obtained under the trade designation “NORZON” from Norton Company, Worcester, Mass.) were used in place of the Example 32 glass-ceramic abrasive particles.

[0242] Comparative Example D coated abrasive discs were prepared as described above except sol-gel-derived abrasive particles (marketed under the trade designation “321 CUBITRON” from the 3M Company, St. Paul, Minn.) was used in place of the Example 32 glass-ceramic abrasive particles.

[0243] The grinding performance of Example 32 and Comparative Examples B-D coated abrasive discs were evaluated as follows. Each coated abrasive disc was mounted on a beveled aluminum back-up pad, and used to grind the face of a pre-weighed 1.25 cm×18 cm×10 cm 1018 mild steel workpiece. The disc was driven at 5,000 rpm while the portion of the disc overlaying the beveled edge of the back-up pad contacted the workpiece at a load of 8.6 kilograms. Each disc was used to grind an individual workpiece in sequence for one-minute intervals. The total cut was the sum of the amount of material removed from the workpieces throughout the test period. The total cut by each sample after 12 minutes of grinding as well as the cut at the 12th minute (i.e., the final cut) are reported in Table 14, below. The Example 32 results are an average of two discs, where as one disk was tested for each of Example 32A, and Comparative Examples B, C, and D. TABLE 14 Example Total cut, g Final cut, g 32 1163 92 32A 1197 92 Comp. B 514 28 Comp. C 689 53 Comp. D 1067 89

[0244] Various modifications and alterations of this invention will become apparent to those skilled in the art without departing from the scope and spirit of this invention, and it should be understood that this invention is not to be unduly limited to the illustrative embodiments set forth herein. 

What is claimed is:
 1. Amorphous material comprising Al₂O₃, ZrO₂, and a metal oxide other than Al₂O₃ or ZrO₂, wherein at least a portion of the metal oxide other than Al₂O₃ or ZrO₂ forms a distinct crystalline phase when the amorphous material is crystallized, wherein the amorphous material comprises at least 50 percent by weight collectively of the Al₂O₃ and the ZrO₂, based on the total weight of the amorphous material, wherein the amorphous material contains not more than 20 percent by weight collectively As₂O₃, B₂O₃, GeO₂, P₂O₅, SiO₂, TeO₂, and V₂O₅, based on the total weight of the amorphous material, wherein the amorphous material has x, y, and z dimensions each perpendicular to each other, and wherein each of the x, y, and z dimensions is at least 25 micrometers.
 2. The amorphous material according to claim 1 wherein the amorphous material does not have a T_(g).
 3. The amorphous material according to claim 1 comprising at least 35 percent by weight Al₂O₃, based on the total weight of the amorphous material.
 4. The amorphous material according to claim 1 comprising Al₂O₃ in a range of about 55 to about 65 percent by weight to a range of about 45 to about 35 percent by weight ZrO₂, based on the total Al₂O₃ and ZrO₂ content of the amorphous material.
 5. The amorphous material according to claim 1 wherein the metal oxide other than Al₂O₃ or ZrO₂ is TiO_(7.)
 6. Ceramic comprising the amorphous material according to claim
 1. 7. The ceramic according to claim 6 wherein the amorphous material is glass.
 8. A method for making amorphous material comprising Al₂O₃, ZrO₂, and a metal oxide other than Al₂O₃ or ZrO₂, wherein at least a portion of the metal oxide other than Al₂O₃ or ZrO₂ forms a distinct crystalline phase when the amorphous material is crystallized, wherein the amorphous material comprises at least 50 percent by weight collectively of the Al₂O₃ and the ZrO₂, based on the total weight of the amorphous material, wherein the amorphous material contains not more than 20 percent by weight collectively As₂O₃, B₂O₃, GeO₂, P₂O₅, SiO₂, TeO₂, and V₂O₅, based on the total weight of the amorphous material, wherein the amorphous material has x, y, and z dimensions each perpendicular to each other, and wherein each of the x, y, and z dimensions is at least 25 micrometers, the method comprising: melting sources of at least Al₂O₃, ZrO₂, and a metal oxide other than Al₂O₃ or ZrO₂ to provide a melt; and cooling the melt to provide the amorphous material.
 9. Glass-ceramic comprising Al₂O₃, ZrO₂, and a metal oxide other than Al₂O₃ or ZrO₂, wherein at least a portion of the metal oxide other than Al₂O₃ or ZrO₂ is present as at least one distinct crystalline phase, wherein the glass-ceramic comprises at least 50 percent by weight collectively of the Al₂O₃ and the ZrO₂, based on the total weight of the glass-ceramic, wherein the glass-ceramic contains not more than 20 percent by weight collectively As₂O₃, B₂O₃, GeO₂, P₂O₅, SiO₂, TeO₂, and V₂O₅, based on the total weight of the glass-ceramic, wherein the glass-ceramic has x, y, and z dimensions each perpendicular to each other, and wherein each of the x, y, and z dimensions is at least 25 micrometers.
 10. A method for making glass-ceramic, the method comprising: heat-treating amorphous material such that at least a portion of the amorphous material is converted to a glass-ceramic, wherein the amorphous material comprises Al₂O₃, ZrO₂, and a metal oxide other than Al₂O₃ or ZrO₂, wherein at least a portion of the metal oxide other than Al₂O₃ or ZrO₂ forms a distinct crystalline phase during the heat-treating, wherein the amorphous material comprises at least 50 percent by weight collectively of the Al₂O₃ and the ZrO₂, based on the total weight of the amorphous material, wherein the amorphous material contains not more than 20 percent by weight collectively As₂O₃, B₂O₃, GeO₂, P₂O₅, SiO₂, TeO₂, and V₂O₅, based on the total weight of the amorphous material, wherein the amorphous material has x, y, and z dimensions each perpendicular to each other, wherein each of the x, y, and z dimensions is at least 25 micrometers, wherein the glass-ceramic comprises Al₂O₃, ZrO₂, and a metal oxide other than Al₂O₃ or ZrO₂, wherein at least a portion of the metal oxide other than Al₂O₃ or ZrO₂ is present as at least one distinct crystalline phase, wherein the glass-ceramic comprises at least 50 percent by weight collectively of the Al₂O₃ and the ZrO₂, based on the total weight of the glass-ceramic, wherein the glass-ceramic contains not more than 20 percent by weight collectively As₂O₃, B₂O₃, GeO₂, P₂O₅, SiO₂, TeO₂, and V₂O₅, based on the total weight of the glass-ceramic, wherein the glass-ceramic has x, y, and z dimensions each perpendicular to each other, and wherein each of the x, y, and z dimensions is at least 25 micrometers.
 11. A plurality of abrasive particles having a specified nominal grade, wherein at least a portion of the abrasive particles is a plurality of abrasive particles comprising a glass-ceramic, wherein the glass-ceramic comprises Al₂O₃, at least 15 percent by weight ZrO₂, based on the total weight of the glass-ceramic of each particle of the portion, and Y₂O₃, wherein at least a portion of the Y₂O₃ is present as at least one distinct crystalline phase.
 12. A plurality of abrasive particles having a specified nominal grade, wherein at least a portion of the abrasive particles is a plurality of abrasive particles comprising a glass-ceramic, wherein the glass-ceramic comprises Al₂O₃, at least 15 percent by weight ZrO₂, based on the total weight of the glass-ceramic of each particle of the portion, and REO, wherein at least a portion of the REO is present as at least one distinct crystalline phase.
 13. A plurality of abrasive particles having a specified nominal grade, wherein at least a portion of the abrasive particles is a plurality of abrasive particles comprising a glass-ceramic, wherein the glass-ceramic comprises Al₂O₃, at least 15 percent by weight ZrO₂, based on the total weight of the glass-ceramic of each particle of the portion, and contains not more than 10 percent by weight collectively As₂O₃, B₂O₃, GeO₂, P₂O₅, SiO₂, TeO₂, and V₂O₅, based on the total weight of the glass-ceramic of each particle of the portion, wherein the glass-ceramic of at least some of the portion of abrasive particles has x, y, and z dimensions each perpendicular to each other, and wherein each of the x, y, and z dimensions is at least 25 micrometers.
 14. A plurality of abrasive particles having a specified nominal grade, wherein at least a portion of the abrasive particles is a plurality of abrasive particles comprising a glass-ceramic, wherein the glass-ceramic comprises Al₂O₃, ZrO₂, and a metal oxide other than Al₂O₃ or ZrO₂, wherein at least a portion of the metal oxide other than Al₂O₃ or ZrO₂ is present as at least one distinct crystalline phase, wherein the glass-ceramic of each particle of the portion collectively comprises at least 50 percent by weight collectively of the Al₂O₃ and the ZrO₂, based on the total weight of the glass-ceramic of each particle of the portion, wherein the glass-ceramic of each particle of the portion contains not more than 20 percent by weight collectively As₂O₃, B₂O₃, GeO₂, P₂O₅, SiO₂, TeO₂, and V₂O₅, based on the total weight of the glass-ceramic of each particle of the portion.
 15. A method for making abrasive particles, the method comprising: providing a plurality of particles having a specified nominal grade, wherein at least a portion of the particles is a plurality of particles comprising an amorphous material, wherein the amorphous material comprises Al₂O₃, ZrO₂, and a metal oxide other than Al₂O₃ or ZrO₂, wherein at least a portion of the metal oxide other than Al₂O₃ or ZrO₂ forms a distinct crystalline phase during heat-treating, wherein the amorphous material comprises at least 50 percent by weight collectively of the Al₂O₃ and the ZrO₂, based on the total weight of the amorphous material, wherein the amorphous material contains not more than 20 percent by weight collectively As₂O₃, B₂O₃, GeO₂, P₂O₅, SiO₂, TeO₂, and V₂O₅, based on the total weight of the amorphous material; and heat-treating the particles comprising amorphous material to provide abrasive particles comprising a glass-ceramic such that at least a portion of the amorphous material is converted to a glass-ceramic and such that a plurality of abrasive particles having a specified nominal grade is provided, wherein at least a portion of the abrasive particles is a plurality of the abrasive particles comprising the glass-ceramic, wherein the glass-ceramic comprises the Al₂O₃, the ZrO₂, and the metal oxide other than Al₂O₃ or ZrO₂, wherein at least a portion of the metal oxide other than Al₂O₃ or ZrO₂ is present as at least one distinct crystalline phase, wherein the glass-ceramic of each particle of the portion collectively comprises at least 50 percent by weight collectively of the Al₂O₃ and the ZrO₂, based on the total weight of the glass-ceramic of each particle of the portion, wherein the glass-ceramic of each particle of the portion contains not more than 20 percent by weight collectively As₂O₃, B₂O₃, GeO₂, P₂O₅, SiO₂, TeO₂, and V₂O₅, based on the total weight of the glass-ceramic of each particle of the portion.
 16. A method for making abrasive particles, the method comprising: heat-treating particles comprising an amorphous material such that at least a portion of the amorphous material is converted to a glass-ceramic, wherein the amorphous material comprises Al₂O₃, ZrO₂, and a metal oxide other than Al₂O₃ or ZrO₂, wherein at least a portion of the metal oxide other than Al₂O₃ or ZrO₂ forms a distinct crystalline phase during the heat-treating, wherein the amorphous material comprises at least 50 percent by weight collectively of the Al₂O₃ and the ZrO₂, based on the total weight of the amorphous material, wherein the amorphous material contains not more than 20 percent by weight collectively As₂O₃, B₂O₃, GeO₂, P₂O₅, SiO₂, TeO₂, and V₂O₅, based on the total weight of the amorphous material, wherein the glass-ceramic comprises the Al₂O₃, the ZrO₂, and the metal oxide other than Al₂O₃ or ZrO₂, wherein at least a portion of the metal oxide other than Al₂O₃ or ZrO₂ is present as at least one distinct crystalline phase, wherein the glass-ceramic of each particle of the portion collectively comprises at least 50 percent by weight collectively of the Al₂O₃ and the ZrO₂, based on the total weight of the glass-ceramic of each particle of the portion, wherein the glass-ceramic of each particle of the portion contains not more than 20 percent by weight collectively As₂O₃, B₂O₃, GeO₂, P₂O₅, SiO₂, TeO₂, and V₂O₅, based on the total weight of the glass-ceramic of each particle of the portion; and grading the abrasive particles comprising the glass-ceramic to provide a plurality of abrasive particles having a specified nominal grade, wherein at least a portion of the plurality of abrasive particles is a plurality of the abrasive particles comprising the glass-ceramic.
 17. A method for making abrasive particles, the method comprising: heat-treating ceramic comprising an amorphous material such that at least a portion of the amorphous material is converted to a glass-ceramic, wherein the amorphous material comprises Al₂O₃, ZrO₂, and a metal oxide other than Al₂O₃ or ZrO₂, wherein at least a portion of the metal oxide other than Al₂O₃ or ZrO₂ forms a distinct crystalline phase during the heat-treating, wherein the amorphous material comprises at least 50 percent by weight collectively of the Al₂O₃ and the ZrO₂, based on the total weight of the amorphous material, wherein the amorphous material contains not more than 20 percent by weight collectively As₂O₃, B₂O₃, GeO₂, P₂O₅, SiO₂, TeO₂, and V₂O₅, based on the total weight of the amorphous material, wherein the glass-ceramic comprises the Al₂O₃, the ZrO₂, and the metal oxide other than Al₂O₃ or ZrO₂, wherein at least a portion of the metal oxide other than Al₂O₃ or ZrO₂ is present as at least one distinct crystalline phase, wherein the glass-ceramic comprises at least 50 percent by weight collectively of the Al₂O₃ and the ZrO₂, based on the total weight of the glass-ceramic, wherein the glass-ceramic contains not more than 20 percent by weight collectively As₂O₃, B₂O₃, GeO₂, P₂O₅, SiO₂, TeO₂, and V₂O₅, based on the total weight of the glass-ceramic; crushing the glass-ceramic to provide abrasive particles comprising the glass-ceramic; and grading the abrasive particles comprising the glass-ceramic to provide a plurality of abrasive particles having a specified nominal grade, wherein at least a portion of the plurality of abrasive particles is a plurality of the abrasive particles comprising the glass-ceramic.
 18. The method according to claim 17 wherein the amorphous material has x, y, and z dimensions each perpendicular to each other, wherein each of the x, y, and z dimensions is at least 25 micrometers, and the glass-ceramic has x, y, and z dimensions each perpendicular to each other, wherein each of the x, y, and z dimensions is at least 25 micrometers.
 19. A method for making abrasive particles, the method comprising: providing a plurality of particles having a specified nominal grade, wherein at least a portion of the particles is a plurality of particles comprising an amorphous material, wherein the amorphous material comprises Al₂O₃, at least 15 percent by weight ZrO₂, based on the total weight of the amorphous material, and Y₂O₃, wherein at least a portion of the Y₂O₃ forms a distinct crystalline phase during heat-treating; and heat-treating the particles comprising amorphous material to provide abrasive particles comprising a glass-ceramic such that at least a portion of the amorphous material is converted to a glass-ceramic and such that a plurality of abrasive particles having a specified nominal grade is provided, wherein at least a portion of the abrasive particles is a plurality of the abrasive particles comprising the glass-ceramic, wherein the glass-ceramic comprises the Al₂O₃, the at least 15 percent by weight ZrO₂, based on the total weight of the glass-ceramic of each particle of the portion, and the Y₂O₃, wherein at least a portion of the Y₂O₃ is present as at least one distinct crystalline phase.
 20. A method for making abrasive particles, the method comprising: heat-treating particles comprising an amorphous material such that at least a portion of the amorphous material is converted to a glass-ceramic, wherein the amorphous material comprises Al₂O₃, at least 15 percent by weight ZrO₂, based on the total weight of the amorphous material, and Y₂O₃, wherein at least a portion of the Y₂O₃ forms a distinct crystalline phase during the heat-treating, wherein the glass-ceramic comprises the Al₂O₃, the at least 15 percent by weight ZrO₂, based on the total weight of the amorphous material, and the Y₂O₃, wherein at least a portion of the Y₂O₃ is present as at least one distinct crystalline phase; and grading the abrasive particles comprising the glass-ceramic to provide a plurality of abrasive particles having a specified nominal grade, wherein at least a portion of the plurality of abrasive particles is a plurality of the abrasive particles comprising the glass-ceramic.
 21. A method for making abrasive particles, the method comprising: heat-treating ceramic comprising an amorphous material such that at least a portion of the amorphous material is converted to a glass-ceramic, wherein the amorphous material comprises Al₂O₃, at least 15 percent by weight ZrO₂, based on the total weight of the amorphous material, and Y₂O₃, wherein at least a portion of the Y₂O₃ forms a distinct crystalline phase during the heat-treating, wherein the glass-ceramic comprises the Al₂O₃, the at least 15 percent by weight ZrO₂, based on the total weight of the amorphous material, and the Y₂O₃, wherein at least a portion of the Y₂O₃ is present as at least one distinct crystalline phase; crushing the glass-ceramic to provide abrasive particles comprising the glass-ceramic; and grading the abrasive particles comprising the glass-ceramic to provide a plurality of abrasive particles having a specified nominal grade, wherein at least a portion of the plurality of abrasive particles is a plurality of the abrasive particles comprising the glass-ceramic.
 22. A method for making abrasive particles, the method comprising: providing a plurality of particles having a specified nominal grade, wherein at least a portion of the particles is a plurality of particles comprising an amorphous material, wherein the amorphous material comprises Al₂O₃, at least 15 percent by weight ZrO₂, based on the total weight of the amorphous material, and REO, wherein at least a portion of the REO forms a distinct crystalline phase during heat-treating; and heat-treating the particles comprising amorphous material to provide abrasive particles comprising a glass-ceramic such that at least a portion of the amorphous material is converted to a glass-ceramic and such that a plurality of abrasive particles having a specified nominal grade is provided, wherein at least a portion of the abrasive particles is a plurality of the abrasive particles comprising the glass-ceramic, wherein the glass-ceramic comprises the Al₂O₃, the at least 15 percent by weight ZrO₂, based on the total weight of the glass-ceramic of each particle of the portion, and the REO, wherein at least a portion of the REO is present as at least one distinct crystalline phase.
 23. A method for making abrasive particles, the method comprising: heat-treating particles comprising an amorphous material such that at least a portion of the amorphous material is converted to a glass-ceramic, wherein the amorphous material comprises Al₂O₃, at least 15 percent by weight ZrO₂, based on the total weight of the amorphous material, and REO, wherein at least a portion of the REO forms a distinct crystalline phase during the heat-treating, wherein the glass-ceramic comprises the Al₂O₃, the at least 15 percent by weight ZrO₂, based on the total weight of the amorphous material, and the REO, wherein at least a portion of the REO is present as at least one distinct crystalline phase; and grading the abrasive particles comprising the glass-ceramic to provide a plurality of abrasive particles having a specified nominal grade, wherein at least a portion of the plurality of abrasive particles is a plurality of the abrasive particles comprising the glass-ceramic.
 24. A method for making abrasive particles, the method comprising: heat-treating ceramic comprising an amorphous material such that at least a portion of the amorphous material is converted to a glass-ceramic, wherein the amorphous material comprises Al₂O₃, at least 15 percent by weight ZrO₂, based on the total weight of the amorphous material, and REO, wherein at least a portion of the REO forms a distinct crystalline phase during the heat-treating, wherein the glass-ceramic comprises the Al₂O₃, the at least 15 percent by weight ZrO₂, based on the total weight of the amorphous material, and the REO, wherein at least a portion of the REO is present as at least one distinct crystalline phase; crushing the glass-ceramic to provide abrasive particles comprising the glass-ceramic; and grading the abrasive particles comprising the glass-ceramic to provide a plurality of abrasive particles having a specified nominal grade, wherein at least a portion of the plurality of abrasive particles is a plurality of the abrasive particles comprising the glass-ceramic.
 25. A method for making abrasive particles, the method comprising: providing a plurality of particles having a specified nominal grade, wherein at least a portion of the particles is a plurality of particles comprising an amorphous material, wherein the amorphous material comprises Al₂O₃, at least 15 percent by weight ZrO₂, based on the total weight of the amorphous material of each particle of the portion, and contains not more than 10 percent by weight collectively As₂O₃, B₂O₃, GeO₂, P₂O₅, SiO₂, TeO₂, and V₂O₅, based on the total weight of the amorphous material of each particle of the portion, wherein the amorphous material of at least some of the portion of particles has x, y, and z dimensions each perpendicular to each other, and wherein each of the x, y, and z dimensions is at least 25 micrometers; and heat-treating the particles comprising the amorphous material to provide abrasive particles comprising a glass-ceramic such that at least a portion of the amorphous material is converted to a glass-ceramic and such that a plurality of abrasive particles having a specified nominal grade is provided, wherein at least a portion of the abrasive particles is a plurality of the abrasive particles comprising the glass-ceramic, wherein the glass-ceramic comprises the Al₂O₃, the at least 15 percent by weight ZrO₂, based on the total weight of the glass-ceramic of each particle of the portion, and contains not more than 10 percent by weight collectively As₂O₃, B₂O₃, GeO₂, P₂O₅, SiO₂, TeO₂, and V₂O₅, based on the total weight of the glass-ceramic of each particle of the portion, wherein the glass-ceramic of at least some of the portion of abrasive particles has x, y, and z dimensions each perpendicular to each other, and wherein each of the x, y, and z dimensions is at least 25 micrometers.
 26. A method for making abrasive particles, the method comprising: heat-treating particles comprising an amorphous material such that at least a portion of the amorphous material is converted to a glass-ceramic, wherein the amorphous material comprises Al₂O₃, at least 15 percent by weight ZrO₂, based on the total weight of the amorphous material of each particle comprising the amorphous material, and contains not more than 10 percent by weight collectively As₂O₃, B₂O₃, GeO₂, P₂O₅, SiO₂, TeO₂, and V₂O₅, based on the total weight of the amorphous material of each particle comprising the amorphous material, wherein the amorphous material of at least some of the particles has x, y, and z dimensions each perpendicular to each other, and wherein each of the x, y, and z dimensions is at least 25 micrometers, wherein the glass-ceramic comprises the Al₂O₃, the at least 15 percent by weight ZrO₂, based on the total weight of the glass-ceramic of each particle comprising the glass-ceramic, and contains not more than 10 percent by weight collectively As₂O₃, B₂O₃, GeO₂, P₂O₅, SiO₂, TeO₂, and V₂O₅, based on the total weight of the amorphous material of each particle of the portion, wherein the glass-ceramic of at least some of the particles has x, y, and z dimensions each perpendicular to each other, and wherein each of the x, y, and z dimensions is at least 25 micrometers; and grading the abrasive particles comprising the glass-ceramic to provide a plurality of abrasive particles having a specified nominal grade, wherein at least a portion of the plurality of abrasive particles is a plurality of the abrasive particles comprising the glass-ceramic.
 27. A method for making abrasive particles, the method comprising: heat-treating ceramic comprising an amorphous material such that at least a portion of the amorphous material is converted to a glass-ceramic, wherein the amorphous material comprises Al₂O₃, at least 15 percent by weight ZrO₂, based on the total weight of the amorphous material, and contains not more than 10 percent by weight collectively As₂O₃, B₂O₃, GeO₂, P₂O₅, SiO₂, TeO₂, and V₂O₅, based on the total weight of the amorphous material, wherein the amorphous material has x, y, and z dimensions each perpendicular to each other, and wherein each of the x, y, and z dimensions is at least 25 micrometers, wherein the glass-ceramic comprises the Al₂O₃, the at least 15 percent by weight ZrO₂, based on the total weight of the glass-ceramic, and contains not more than 10 percent by weight collectively As₂O₃, B₂O₃, GeO₂, P₂O₅, SiO₂, TeO₂, and V₂O₅, based on the total weight of the glass-ceramic, wherein the glass-ceramic has x, y, and z dimensions each perpendicular to each other, and wherein each of the x, y, and z dimensions is at least 25 micrometers; crushing the glass-ceramic to provide abrasive particles comprising the glass-ceramic; and grading the abrasive particles comprising the glass-ceramic to provide a plurality of abrasive particles having a specified nominal grade, wherein at least a portion of the plurality of abrasive particles is a plurality of the abrasive particles comprising the glass-ceramic.
 28. A method of abrading a surface, the method comprising: providing an abrasive article comprising a binder and a plurality of abrasive particles, wherein at least a portion of the abrasive particles is a plurality of abrasive particles comprising a glass-ceramic, wherein the glass-ceramic comprises Al₂O₃, at least 15 percent by weight ZrO₂, based on the total weight of the glass-ceramic of each particle of the portion, and Y₂O₃, wherein at least a portion of the Y₂O₃ is present as at least one distinct crystalline phase; contacting at least one of the abrasive particles comprising the glass-ceramic with a surface of a workpiece; and moving at least one of the contacted abrasive particles comprising the glass-ceramic or the contacted surface to abrade at least a portion of the surface with the contacted abrasive particles comprising the glass-ceramic.
 29. A method of abrading a surface, the method comprising: providing an abrasive article comprising a binder and a plurality of abrasive particles, wherein at least a portion of the abrasive particles is a plurality of abrasive particles comprising a glass-ceramic, wherein the glass-ceramic comprises Al₂O₃, at least 15 percent by weight ZrO₂, based on the total weight of the glass-ceramic of each particle of the portion, and REO, wherein at least a portion of the REO is present as at least one distinct crystalline phase; contacting at least one of the abrasive particles comprising the glass-ceramic with a surface of a workpiece; and moving at least one of the contacted abrasive particles comprising the glass-ceramic or the contacted surface to abrade at least a portion of the surface with the contacted abrasive particles comprising the glass-ceramic.
 30. A method of abrading a surface, the method comprising: providing an abrasive article comprising a binder and a plurality of abrasive particles, wherein at least a portion of the abrasive particles is a plurality of abrasive particles comprising a glass-ceramic, wherein the glass-ceramic comprises Al₂O₃, at least 15 percent by weight ZrO₂, based on the total weight of the glass-ceramic of each particle comprising the glass-ceramic of each particle of the portion, and contains not more than 10 percent by weight collectively As₂O₃, B₂O₃, GeO₂, P₂O₅, SiO₂, TeO₂, and V₂O₅, based on the total weight of the glass-ceramic of each particle comprising the glass-ceramic of each particle of the portion, wherein the glass-ceramic of at least some of the particles has x, y, and z dimensions each perpendicular to each other, and wherein each of the x, y, and z dimensions are at least 25 micrometers; contacting at least one of the abrasive particles comprising the glass-ceramic with a surface of a workpiece; and moving at least one of the contacted abrasive particles comprising the glass-ceramic or the contacted surface to abrade at least a portion of the surface with the contacted abrasive particles comprising the glass-ceramic.
 31. A method of abrading a surface, the method comprising: providing an abrasive article comprising a binder and a plurality of abrasive particles, wherein at least a portion of the abrasive particles is a plurality of abrasive particles comprising a glass-ceramic, wherein the glass-ceramic comprises Al₂O₃, ZrO₂, and a metal oxide other than Al₂O₃ or ZrO₂, wherein at least a portion of the metal oxide other than Al₂O₃ or ZrO₂ is present as at least one distinct crystalline phase, wherein the glass-ceramic of each particle of the portion collectively comprises at least 50 percent by weight collectively of the Al₂O₃ and the ZrO₂, based on the total weight of the glass-ceramic, wherein the glass-ceramic of each particle of the portion contains not more than 20 percent by weight collectively As₂O₃, B₂O₃, GeO₂, P₂O₅, SiO₂, TeO₂, and V₂O₅, based on the total weight of the glass-ceramic, wherein the glass-ceramic of at least some of the portion of abrasive particles has x, y, and z dimensions each perpendicular to each other, and wherein each of the x, y, and z dimensions are at least 25 micrometers; contacting at least one of the abrasive particles comprising the glass-ceramic with a surface of a workpiece; and moving at least one of the contacted abrasive particles comprising the glass-ceramic or the contacted surface to abrade at least a portion of the surface with the contacted abrasive particles comprising the glass-ceramic. 